Process for the preparation of high molecular lactic copolymer polyester

ABSTRACT

A novel process for the preparation of a high molecular lactic copolymer polyester is provided, which includes allowing a lactide (A), a polyester terminated by hydroxyl group at both ends (B1), a polyvalent carboxylic acid having 3 or more functionalities and/or acid anhydride thereof (C) to undergo ring opening copolymerization in the presence of a ring opening polymerization catalyst (D). A novel process is also provided which includes allowing the lactide (A) and the polyester (B1) to undergo ring opening copolymerization in the presence of the catalyst (D) to prepare a polyester, and then reacting the polyester with the component (C). A novel process is further provided which includes reacting the polyester (B1) with the polyvalent carboxylic acid component (C) to obtain a polyester terminated by hydroxyl group at both ends having a weight-average molecular weight of from 10,000 to 300,000 (B2), and then allowing the polyester (B2) and the lactide (A) to undergo ring opening copolymerization in the presence of the catalyst (D). Another novel process is provided which includes allowing a dicarboxylic acid, a diol and the polyvalent carboxylic acid component (C) to undergo dehydration reaction and/or deglycolation reaction to obtain a polyester having a weight-average molecular weight of from 10,000 to 300,000 (B3), and then allowing the polyester (B3) and the lactide (A) to undergo ring opening copolymerization in the presence of the catalyst (D).

FIELD OF THE INVENTION

The present invention relates to a process for the preparation of a highmolecular lactic copolymer polyester which comprises reacting apolyfunctional polyvalent carboxylic acid (or its acid anhydride) orpolyfunctional polyvalent isocyanate in the preparation of a lacticcopolymer to prepare a lactic copolymer having a higher molecular weightwhile arbitrarily varying the proportion and kind of the polyester to beincorporated as a starting material in the lactic copolymer to preparehigh molecular lactic copolymer polyesters having different properties.

The lactic copolymer according to the present invention isbiodegradable. The lactic copolymer according to the present inventioncan be subjected to various forming or molding processes such asextrusion molding, injection molding, blow molding and press molding.Thus, the lactic copolymer according to the present invention can besubjected to forming or molding by means of any existing apparatus foruse with general-purpose resins. The lactic copolymer according to thepresent invention is useful as molding resin, coating resin, ink resin,adhesive resin, etc., particularly as molding resin for wrappingmaterial.

Examples of the product worked from extruded sheet of the lacticcopolymer of the present invention include tray, cup, cover, andblister. Examples of the product worked from the film of the lacticcopolymer of the present invention include lap wrapping material, shrinkwrapping material, stretch wrapping material, and bag such as trash bag,supermarket bag, standard bag and double bag. Examples of the extrudedproducts which can be used as agricultural or fishing materials includeagricultural multi-ply film, pesticide-releasing sheet, fowl net, curingnet, sapling pot, fishing net, laver farming net, and fishing line.Examples of the extruded products which can be used as sanitary productsinclude paper diaper, and sanitary napkin. Examples of the extrudedproducts which can be used as medical products include artificialkidney, and stitching fiber. Examples of the blow-molded products towhich the present invention can apply include shampoo bottle, cosmeticsbottle, drink bottle, and oil vessel. Examples of the paper laminates towhich the present invention can apply include tray, one-way vessel suchas cup, and megaphone body.

Examples of the injection-molded products to which the present inventioncan apply include golf tee, applicator's core, candy's stick, brush,toothbrush, injector's cylinder, cover, dish, cup, comb, razor's haft,cassette of recording tape, disposable spoon and folk, and stationarysuch as ball point pen.

Other examples of the molded products to which the present invention canapply include binding tape, prepaid card, balloon, panty hose, hair cap,sponge, cellophane tape, umbrella, raincoat, plastic glove, rope, tube,foamed tray, foamed buffer, buffer, packing material, hot-melt adhesive,cigarette filter, and paint for ship bottom.

BACKGROUND OF THE INVENTION

In recent years, extensive studies have been made to put a lacticpolymer having an excellent biodegradability into wide application as ageneral-purpose polymer. Many studies have been made of process for thepreparation of such a lactic polymer. Further, many proposals for theprocess for the preparation of such a lactic polymer have been appliedfor patent. However, the conventional lactic acid or polylactic acidwhich is a polymer of lactides, or copolymer of lactide with othermonomers leave something to be desired in formability or moldability andtransparency. The polylactic acid is disadvantageous in that itdecomposes too fast to handle as a general-purpose resin except inspecial applications. It has thus been keenly desired to improve thesepolylactic polymers.

International Disclosure No. WO 91/02015 discloses copolymers of anaromatic polyester such as polyethylene terephthalate and polybutyleneterephthalate with polyglycolide or polylactic acid and processes forthe preparation thereof.

The preparation processes disclosed in the above cited patent include aprocess which comprises the reaction of monomers, i.e., lactide,butylene glycol and dimethyl terephthalate, and a process whichcomprises the reaction of polymers, i.e., ester exchange reaction of twopolymers, i.e., polyglycolide and polybutylene terephthalate, at atemperature as high as 220° C. However, preparation processes describedin the examples are limited to the ester exchange reaction of polymers.

JP-A-4-504731 (The term "JP-A" as used herein means an "unexaminedpublished Japanese patent application") discloses a process whichcomprises the polymerization of a lactide with a polyethyleneterephthalate to prepare a blend polymer of a polylactic acid with apolyethylene terephthalate. Further, a technique for reacting acrystalline aromatic polyester with a lactone is disclosed inJP-B-48-4115 (The term "JP-B" as used herein means an "examined Japanesepatent publication") and JP-B-48-4116. In accordance with these methods,a crystalline aromatic polyester is reacted with a lactone, particularlyε-caprolactone or γ-valerolactone.

However, the process disclosed in JP-A-4-504731 is disadvantageous inthat the softening point of the polyethylene terephthalate is as high asnot lower than 220° C., which is higher than the decompositiontemperature of the lactide (185° C.), giving a remarkably coloredcopolymer having an insufficient molecular weight. Further, the processwhich comprises the reaction of lactones disclosed in JP-B-48-4115 andJP-B-48-4116 is disadvantageous in that the resulting copolymer isopaque and flexible and thus is not preferred as a molding resin.

It is generally well known that the preparation process which comprisesthe reaction of monomers, i.e., the reaction of a dicarboxylic acidcomponent or its esterified product with a diol component and a cyclicester such as lactide, cannot provide a higher molecular weight.Further, the preparation process which comprises the reaction ofpolymers is impractical in that the decomposition temperature of thepolylactic acid is much lower than the temperature at which the aromaticpolyester such as polyethylene terephthalate and polybutyleneterephthalate becomes fluid.

Moreover, the resulting lactic copolymer polyester is brittle andexhibits a poor transparency because the aromatic polyester iscrystalline and exhibits a high melt temperature and a poorcompatibility with other compounds. JP-A-63-145661 proposes a processfor the preparation of a copolymer of a lactide with an aliphaticpolyester which comprises the polymerization of ε-caprolactone to obtaina homopolymer which is then block-copolymerized with a lactide.

However, the above-proposed process which comprises the blockcopolymerization of a poly(ε-caprolactone) with a lactide isdisadvantageous in that the resulting copolymer becomes cloudy andopaque. This is probably because that the poly(ε-caprolactone) block andthe polylactic acid block in the copolymer are hardly compatible witheach other and the aliphatic polyester in the poly(ε-caprolactone) chainreflects a high crystallinity to opacify the copolymer. Further, thecopolymer thus obtained normally stays flexible despite of itsrelatively high glass transition point determined by differentialthermal analysis.

To summarize these conventional techniques, polymers provided with asufficient strength, heat resistance and thermal stability exhibit aninsufficient flexibility and transparency. On the contrary, polymersprovided with a sufficient flexibility and transparency exhibit aninsufficient strength, heat resistance and thermal stability. Thus,polymers provided with properties satisfactory enough for resins to beformed into film or sheet have not yet been obtained.

Further, if a lactide to be incorporated as a residual monomer is usedas a plasticizer to plasticize the polymer, the remaining lactidesublimates, scatters and then attaches itself to the apparatus duringpreparation, contaminating the apparatus. Moreover, the lactidedisappears from the polymer during storage or while in use, the desiredplasticizing effect disappears and things wrapped by the wrappingmaterial can be contaminated.

If an ordinary plasticizer is used instead of lactide, it must be usedin a large amount to attain a sufficient plasticizing effect. Thus, theplasticizer unavoidably bleeds out, and the problems such as thedisappearance of the desired plasticizing effect during storage and thecontamination of things wrapped by the wrapping material could not besolved. Accordingly, polymers provided with properties satisfactoryenough for the application as wrapping materials have not yet beenobtained.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a processfor the preparation of a decomposable lactic copolymer polyester whichexhibits a sufficiently high molecular weight, heat resistance andthermal stability and further exhibits a rigidity, flexibility andtransparency depending on the purpose.

The foregoing object of the present invention will become more apparentfrom the following detailed description and examples.

The inventors made extensive studies to solve these problems. As aresult, the following knowledges were obtained.

In some detail, the following processes are proposed:

A process which comprises the reaction, as essential components, of alactide and a polyester comprising an aliphatic dicarboxylic acidcomponent and/or aromatic dicarboxylic acid component and/or polyvalentcarboxylic acid component having 3 or more functionalities and a diolcomponent in various formulations;

A process which comprises the reaction, as essential components, of alactide, a polyester comprising an aliphatic dicarboxylic acid componentand/or aromatic dicarboxylic acid component and a diol component invarious formulations and a polyvalent carboxylic acid having 3 or morefunctionalities;

A process which comprises the reaction, as essential components, of apolyester obtained by the reaction of a polyester comprising analiphatic dicarboxylic acid component and/or aromatic dicarboxylic acidcomponent and a diol component in various formulations and a polyvalentisocyanate having 2 or more functionalities and a lactide; or

A process which comprises the reaction, as essential components, of alactic copolymer polyester obtained by the reaction of a lactide with apolyester comprising an aliphatic dicarboxylic acid component and/oraromatic dicarboxylic acid component and a diol component in variousformulations and a polyvalent isocyanate having 3 or morefunctionalities.

In accordance with the foregoing proposed processes, the decompositionof the monomers during forming or molding can be controlled. Forming andmolding can be effected at wider temperature ranges. Further, theresulting polymer can be provided with a higher molecular weight.Accordingly, the polymer thus obtained can be provided with a higherstrength and a higher thermal stability during forming or molding.

Further, the copolymerization of a hard hydrolyzable polylactic acidwith a hydrophobic polyester can provide a less hydrolyzable polymer.Moreover, the proportion of the aliphatic dicarboxylic acid componentand the aromatic dicarboxylic acid component can be arbitrarily variedor the proportion of the polyester to be copolymerized with thesecomponents can be arbitrarily varied to prepare various lactic polyesterproducts ranging from a hard resin having a high glass transition pointand melting point to a rigid and highly flexible resin having a tenacitywhich can be formed into a film that exhibits a high tear strength andcan hardly be cracked.

Still further, the use of the polyvalent carboxylic acid having 3 ormore functionalities or polyvalent isocyanate having 2 or morefunctionalities makes it easier to provide a higher molecular weight.This makes it possible to arbitrarily select the kind and proportion ofcopolymer polyesters. Accordingly, a decomposable high molecular lacticpolyester can be obtained which exhibits a strength and molding thermalstability high enough for the application as a general-purpose resin andexhibits a sufficient rigidity, transparency and flexibility dependingon the purpose. Thus, the present invention has been worked out.

The present invention concerns (1) a process for the preparation of ahigh molecular lactic copolymer polyester, which comprises allowing alactide (A), a polyester terminated by hydroxyl group at both ends (B1),a polyvalent carboxylic acid having 3 or more functionalities and/oracid anhydride thereof (C) to undergo ring opening copolymerization insuch an amount that the weight ratio of (A)/(B1) is from 50/50 to 98/2and the proportion of the component (C) is from 0.001 to 5% by weight ofthe sum of the amount of the components (A) and (B1) in the presence ofa ring opening polymerization catalyst (D).

The present invention also concerns (2) a process for the preparation ofa high molecular lactic copolymer polyester, which comprises allowing alactide (A) and a polyester terminated by hydroxyl group at both ends(B1) to undergo ring opening copolymerization in (A)/(B1) weight ratioof 50/50 to 98/2 in the presence of a ring opening polymerizationcatalyst (D) to prepare a polyester, and then reacting said polyesterwith a polyvalent carboxylic acid having 3 or more functionalitiesand/or acid anhydride thereof (C) in such an amount that the proportionof the component (C) is from 0.001 to 5% by weight of the sum of theamount of the components (A) and (B1).

The present invention further concerns (3) a process for the preparationof a high molecular lactic copolymer polyester, which comprises reactinga polyester terminated by hydroxyl group at both ends (B1) with apolyvalent carboxylic acid having 3 or more functionalities and/or acidanhydride thereof (C) in such an amount that the proportion of thecomponent (C) is from 0.001 to 5% by weight of the amount of thecomponent (B1) to obtain a polyester terminated by hydroxyl group atboth ends having a weight-average molecular weight of from 10,000 to300,000 (B2), and then allowing said polyester (B2) and a lactide (A) toundergo ring opening copolymerization in such an amount that the weightratio of (A)/(B2) is from 50/50 to 98/2 in the presence of a ringopening polymerization catalyst (D).

The present invention concerns (4) a process for the preparation of ahigh molecular lactic copolymer polyester, which comprises allowing adicarboxylic acid, a diol and a polyvalent carboxylic acid having 3 ormore functionalities and/or acid anhydride thereof (C) in an amount offrom 0.001 to 5% by weight to undergo dehydration reaction and/ordeglycolation reaction to obtain a polyester having a weight-averagemolecular weight of from 10,000 to 300,000 (B3), and then allowing saidpolyester (B3) and a lactide (A) to undergo ring openingcopolymerization in such an amount that the weight ratio of (A)/(B3) isfrom 50/50 to 98/2 in the presence of a ring opening polymerizationcatalyst (D).

The present invention still further concerns the process for thepreparation of a high molecular lactic copolymer polyester as definedabove, wherein the polyester terminated by hydroxyl group at both ends(B1) has a weight-average molecular weight of 10,000 to 200,000 and thepolyvalent carboxylic acid having 3 or more functionalities and/or acidanhydride thereof (C) is selected from the group consisting oftrimellitic acid, trimellitic anhydride, pyromellitic acid andpyromellitic anhydride.

The present invention concerns a process for the preparation of a highmolecular lactic copolymer polyester, which comprises reacting apolyester terminated by hydroxyl group at both ends (B1) with apolyvalent isocyanate (E) having 2 or more functionalities in such anamount that the proportion of the component (E) is from 0.01 to 5% byweight of the amount of the polyester (B1) to obtain a polyester (B4)having a weight-average molecular weight of from 10,000 to 300,000, andthen allowing said polyester (B4) and lactide (A) to undergo ringopening copolymerization in such an amount that the weight ratio of(A)/(B4) is from 50/50 to 98/2 in the presence of a ring openingpolymerization catalyst (D).

The present invention further concerns a process for the preparation ofa high molecular lactic copolymer polyester, which comprises allowing alactide (A) and a polyester terminated by hydroxyl group at both ends(B1) to undergo ring opening copolymerization in such an amount that theweight ratio of (A)/(B1) is from 50/50 to 98/2 in the presence of a ringopening polymerization catalyst (D) to prepare a polyester having aweight-average molecular weight of from 10,000 to 300,000, and thenreacting said polyester with a polyvalent isocyanate having 3 or morefunctionalities in such an amount that the proportion of said polyvalentisocyanate (F) is from 0.01 to 5% by weight of the sum of the amount ofthe components (A) and (B1).

The present invention still further concerns the process for thepreparation of a high molecular lactic copolymer polyester as definedabove, wherein the polyester terminated by hydroxyl group at both ends(B1) has a weight-average molecular weight of from 10,000 to 200,000.

The present invention concerns the process for the preparation of a highmolecular lactic copolymer polyester as defined above, wherein theresulting high molecular lactic copolymer polyester has a weight-averagemolecular weight of from 20,000 to 600,000.

The present invention also concerns the process for the preparation of ahigh molecular lactic copolymer polyester as defined above, wherein astatic mixer is used as a polymerization reaction vessel and acontinuous polymerization apparatus comprising a series connection oftwo or more agitated reaction vessels is used.

Moreover, the present invention concerns a formed or molded product of ahigh molecular lactic copolymer polyester prepared by the preparationprocess as defined above.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be further described hereinafter.

The lactide, polyester terminated by hydroxyl group at both ends,polyvalent carboxylic acid having 3 or more functionalities,diisocyanate and polyvalent isocyanate having 3 or more functionalitiesas used herein will be sequentially further described hereinafter.

The lactide employable in the present invention is a compound obtainedby the cyclic esterification of lactic acid between two molecules of theacid or a monomer having stereoisomers. Examples of the lactideemployable in the present invention include L-lactide made of twoL-lactic acids, D-lactide made of two D-lactic acids, and MESO-lactidemade of L-lactic acid and D-lactic acid.

A copolymer comprising L-lactide or D-lactide alone crystallizes toexhibit a high melting point. The high molecular lactic polyester of thepresent invention comprises these three lactides in combination torealize desirable resin properties corresponding to the purpose.

In order to realize high thermophysical properties, the content ofL-lactide is preferably not less than 75% of the total content oflactides. In order to realize still higher thermophysical properties,the content of L-lactide is preferably not less than 90% of the totalcontent of lactides.

Examples of the polyester terminated by hydroxyl group at both ends (B)employable in the present invention include aromatic polyester made ofaromatic dicarboxylic acid component and diol component, aliphaticpolyester made of aliphatic dicarboxylic acid component and diolcomponent, and aliphatic aromatic polyester made of aliphaticdicarboxylic acid component, aromatic dicarboxylic acid component anddiol component.

The aromatic dicarboxylic acid component to be incorporated in thepolyester employable in the present invention is not specificallylimited. Specific examples of the aromatic dicarboxylic acid componentinclude phthalic acid, isophthalic acid, terephthalic acid,naphthalenedicarboxylic acid, and phthalic anhydride. Other examples ofthe aromatic dicarboxylic acid component include esters of alcohols anddiols with phthalic acid, isophthalic acid, terephthalic acid,naphthalenedicarboxylic acid, etc.

The aliphatic dicarboxylic acid component to be incorporated in thepolyester employable in the present invention is not specificallylimited. A C₄₋₁₄ aliphatic dicarboxylic acid is particularly preferred.Specific examples of such an aliphatic dicarboxylic acid includesuccinic acid, adipic acid, azelaic acid, sebacic acid, brassylic acid,and cyclohexanedicarboxylic acid. Besides these aliphatic dicarboxylicacids, dimer acids can be used.

As the diol component to be incorporated in the polyester there may beused any diol. Particularly preferred among these diols is a C₂₋₁₀ diol.Specific examples of such a diol include ethylene glycol, propyleneglycol, butylene glycol, pentanediol, hexamethylene glycol, octanediol,neopentyl glycol, cyclohexanedimethanol, xylene glycol, diethyleneglycol, triethylene glycol, dipropylene glycol, dibutanediol,3-hydroxydipivalyl pivalate, and hydrogenated bisphenol A.

In order to enhance the transparency of the copolymer thus obtained,neopentyl glycol is preferably incorporated therein in an amount of notless than 20% by weight of the diol content. The molar ratio of thedicarboxylic acid component to the diol component is preferably about 1.

The high molecular lactic copolymer polyester obtained according to thepresent invention can be formed into a sheet having a strength rangingfrom a high value to a low value (flexible sheet). In some detail, asheet having a tensile viscoelasticity of from 500 to 50,000 kg/cm² canbe obtained.

In the present invention, both the aromatic polyester and the aliphaticpolyester free of aromatic ring can be used as starting materials. Inthis case, too, both the polyesters preferably have a weight-averagemolecular weight as high as not less than 1,000, particularly from10,000 to 200,000.

The weight ratio of the aromatic polyester to the aliphatic polyester isnot limited. In order to maintain a practically sufficient strength,flexibility and transparency, the content of the aromatic polyester andthe aliphatic polyester are preferably from 1 to 49 parts by weight andfrom 1 to 49 parts by weight based on 100 parts by weight of the sum ofthe amount of the aromatic polyester and the aliphatic polyester,respectively.

The aromatic polyester, aliphatic polyester and aromatic aliphaticpolyester employable in the present invention each preferably exhibit amelting point or softening point, whichever lower, of not higher than200° C., particularly from 80° to 190° C. The aromatic polyester may beeither crystalline or amorphous but is preferably transparent.

A commercially available polyethylene terephthalate for general purposenormally exhibits a softening point of 220° to 255° C. that is notsuited for the preparation process of the present invention. When aspecial polyethylene terephthalate having a softening point as low asnot higher than 200° C. is used in the process for the preparation ofthe copolymer of the present invention, a non-colored high molecularexcellent lactic copolymer can be obtained. The melting point as definedherein is determined by differential scanning calorimetric analysis(DSC).

In the present invention, a high molecular lactic polyester having ahigher molecular weight can be provided by subjecting at least onepolyvalent carboxylic acid and/or acid anhydride thereof in combinationto esterification. Further, since branches are introduced into thepolyester, the molecular-weight distribution of the polyester iswidened. Moreover, a metal reacts with a carboxyl group having 1 or morefunctionalities in the polyvalent carboxylic acid and/or acid anhydridethereof to ionomerize the polymer. As a result, the polyester can beformed into a film or sheet having excellent physical properties.

Examples of the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof include trimesic acid,propanetricarboxylic acid, trimellitic acid, trimellitic anhydride,pyromellitic acid, pyromellitic anhydride, benzophenonetetracarboxylicanhydride, cyclopentatetracarboxylic anhydride,1,3,5-cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid,and cyclohexanetetracarboxylic anhydride. Particularly preferred amongthese compounds are trimellitic anhydride, and pyromellitic anhydride.These polyvalent carboxylic acid and/or acid anhydride thereof may beused in admixture as necessary.

The polyfunctional isocyanate as used herein preferably has two or moreisocyanate groups, particularly only isocyanate groups as functionalgroups. In order that the resulting urethane bond-containing lacticpolyester substantially has a linear structure, a bifunctionalisocyanate is preferred.

Specific examples of such an isocyanate include hexamethylenediisocyanate, tolylene-2,4-diisocyanate, tolylene-2,5-diisocyanate,toluene diisocyanate, xylylene diisocyanate, diphenylmethanediisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate,hydrogenated diphenylmethane diisocyanate, diisocyanate-modifiedpolyether, diisocyanate-modified polyester, and mixture thereof.

In order to obtain an urethane-containing lactic copolymer polyesterwhich exhibits a high thermal stability during formation, apolyfunctional isocyanate having 3 or more functionalities can bepreferably used in particular.

In this case, the resulting polymer is branched. In order to obtain sucha polymer, a compound obtained by modifying a polyvalent alcohol by abifunctional isocyanate, e.g., bifunctional isocyanate-modifiedpentaerythritol, the foregoing polyvalent isocyanate-modified polyether,similar polyvalent isocyanate-modified polyester, etc. can be used.

As the polyfunctional isocyanate (E) employable in the present inventionthere can be used a combination of several polyfunctional isocyanates.For example, a small amount of an isocyanate having 3 or morefunctionalities may be used in combination with a bifunctionalisocyanate to cause reaction without gelation, making it possible toprovide a higher molecular weight.

Preferred conditions of the polyester terminated by hydroxyl group atboth ends, the polyvalent carboxylic acid having 3 or morefunctionalities, the diisocyanate, the polyvalent isocyanate having 3 ormore functionalities and the desired high molecular lactic copolymerpolyester according to the present invention will be describedhereinafter.

The polyester terminated by hydroxyl group at both ends (B1) preferablyhas a weight-average molecular weight of from 10,000 to 200,000 or anumber-average molecular weight of from 5,000 to 100,000 for the purposeof increasing the molecular weight of the resulting lactic copolymer.

From the standpoint of the solubility and ease of preparation of thepolyester terminated by hydroxyl group at both ends, the polyesterterminated by hydroxyl group at both ends (B1) preferably has aweight-average molecular weight of from 20,000 to 100,000 or anumber-average molecular weight of from 10,000 to 50,000.

The ratio of the lactide (A) to the polyester terminated by hydroxylgroup at both ends (B1) is preferably from 50/50 to 98/2 to raise themolecular weight of the resulting high molecular lactic copolymer. Morepreferably, the ratio of (A)/(B1) is from 65/35 to 98/2 to enhance thetransparency of the resulting high molecular lactic copolymer.

The proportion of the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C) in the preparationprocess as defined above (1) and (2) is preferably from 0.001 to 5% byweight based on 100% by weight of the sum of the amount of the lactide(A) and the polyester terminated by hydroxyl group at both ends (B1).More preferably, the proportion of the polyvalent carboxylic acid having3 or more functionalities and/or acid anhydride thereof (C) is from0.001 to 0.1% by weight to enhance the molecular weight and flexibilityof the resulting high molecular lactic copolymer.

The polyester terminated by hydroxyl group at both ends (B2) obtained bythe reaction of the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C) with the polyesterterminated by hydroxyl group at both ends (B1) preferably has aweight-average molecular weight of from 10,000 to 300,000 for thepurpose of increasing the molecular weight of the resulting lacticcopolymer.

From the standpoint of the solubility and ease of preparation of thepolyester terminated by hydroxyl group at both ends, the polyesterpreferably has a weight-average molecular weight of from 20,000 to150,000 or a number-average molecular weight of from 10,000 to 80,000.

The ratio of the lactide (A) to the polyester terminated by hydroxylgroup at both ends (B2) is preferably from 50/50 to 98/2 to raise themolecular weight of the resulting high molecular lactic copolymer. Morepreferably, the ratio of (A)/(B2) is from 65/35 to 98/2 to enhance thetransparency of the resulting high molecular lactic copolymer.

The proportion of the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C) in the preparationprocess as defined above (3) is preferably from 0.001 to 5% by weightbased on 100% by weight of the polyester terminated by hydroxyl group atboth ends (B1). More preferably, the proportion of the polyvalentcarboxylic acid having 3 or more functionalities and/or acid anhydridethereof (C) is from 0.001 to 0.1% by weight, particularly from 0.001 to0.1% by weight to enhance the molecular weight and flexibility of theresulting high molecular lactic copolymer.

The high molecular polyester terminated by hydroxyl group at both ends(B3) obtained by allowing the polyvalent carboxylic acid having 3 ormore functionalities and/or acid anhydride thereof (C), the dicarboxylicacid and the diol to undergo dehydration reaction and deglycolationreaction preferably has a weight-average molecular weight of from 10,000to 300,000 or a number-average molecular weight of from 10,000 to100,000 for the purpose of increasing the molecular weight of theresulting lactic copolymer.

More preferably, the resulting high molecular polyester (B3) has aweight-average molecular weight of from 20,000 to 150,000 or anumber-average molecular weight of from 10,000 to 50,000 from thestandpoint of the solubility and ease of preparation thereof.

The ratio of the lactide (A) to the polyester terminated by hydroxylgroup at both ends (B3) is preferably from 50/50 to 98/2 to raise themolecular weight of the resulting high molecular lactic copolymer. Morepreferably, the ratio of (A)/(B3) is from 65/35 to 98/2 to enhance thetransparency of the resulting high molecular lactic copolymer.

The proportion of the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C) in the polyesterterminated by hydroxyl group at both ends (B3) is preferably from 0.001to 5% by weight based on 100% by weight of the total weight of thedicarboxylic acid or acid anhydride thereof. More preferably, theproportion of the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C) is from 0.01 to 1% byweight to enhance the molecular weight and flexibility of the resultinghigh molecular lactic copolymer.

The polyester (B4) obtained by the reaction of the polyester terminatedby hydroxyl group at both ends (B1) with the polyvalent isocyanatehaving 2 or more functionalities (E) preferably has a weight-averagemolecular weight of from 10,000 to 300,000 or a number-average molecularweight of from 10,000 to 100,000 for the purpose of increasing themolecular weight of the resulting lactic copolymer.

More preferably, the resulting high molecular polyester (B4) has aweight-average molecular weight of from 20,000 to 150,000 or anumber-average molecular weight of from 10,000 to 50,000 from thestandpoint of the solubility and ease of preparation thereof.

The ratio of the lactide (A) to the polyester terminated by hydroxylgroup at both ends (B4) containing the polyvalent isocyanate having 2 ormore functionalities (E) is preferably from 50/50 to 98/2 to raise themolecular weight of the resulting high molecular lactic copolymerpolyester. More preferably, the ratio of (A)/(B4) is from 65/35 to 98/2to enhance the transparency of the resulting high molecular lacticcopolymer.

The proportion of the polyvalent isocyanate having 2 or morefunctionalities (E) is preferably from 0.01 to 5% by weight based on theweight of the polyester terminated by hydroxyl group at both ends (B1).More preferably, the proportion of the polyvalent isocyanate having 2 ormore functionalities (E) is from 0.1 to 3% by weight to enhance themolecular weight and flexibility of the resulting high molecular lacticcopolymer.

In the case where the lactide (A) and the polyester terminated byhydroxyl group at both ends (B1) are allowed to undergo ring openingcopolymerization in the presence of a ring opening polymerizationcatalyst (D) to prepare a polyester having a weight-average molecularweight of from 10,000 to 300,000 which is then reacted with a polyvalentisocyanate having 3 or more functionalities (F), the proportion of thepolyvalent isocyanate having 3 or more functionalities (F) is preferablyfrom 0.01 to 5% by weight, more preferably from 0.1 to 3% by weightbased on the sum of the amount of the lactide (A) and the polyesterterminated by hydroxyl group at both ends (B1) to raise the molecularweight and flexibility of the resulting high molecular lactic copolymer.

The desired high molecular lactic copolymer polyester preferably has aweight-average molecular weight of from 20,000 to 600,000 or anumber-average molecular weight of from 10,000 to 300,000. Taking intoaccount the fact that the high molecular lactic copolymer polyesterexhibits a reduced molecular weight when formed or molded, theworkability thereof or the physical properties such as strength of theformed or molded product, the high molecular lactic copolymer polyesterpreferably has a weight-average molecular weight of from 50,000 to500,000 or a number-average molecular weight of from 30,000 to 250,000.

The polymerization reaction is preferably effected in the presence of aring opening polymerization catalyst (D). Examples of the ring openingpolymerization catalyst (D) employable in the present invention includecyclic ester ring opening polymerization catalysts, metals such as tin,zinc, lead, titanium, bismuth, zirconium and germanium and derivativesthereof which are known as ester exchange catalysts, etc. These metalderivatives can be used as catalysts of the present invention.Particularly preferred among these metal derivatives are organicmetallic compounds, metallic carbonates, metallic oxides, metallichalides, etc. Specific examples of these metal derivatives include tinoctanoate, tin chloride, zinc chloride, zinc acetate, lead oxide, leadcarbonate, titanium chloride, alkoxytitanium, germanium oxide, andzirconium oxide.

The amount of the ring opening polymerization catalyst (D) is preferablyfrom 0.005 to 0.2% by weight based on 100% by weight of the sum of theamount of the lactide (A) and the polyester terminated by hydroxyl groupat both ends ((B1), (B2), (B3), or (B4)) and/or the polyvalentcarboxylic acid having 3 or more functionalities and/or acid anhydridethereof (C) or the polyvalent isocyanate having 2 or morefunctionalities (E) or the polyvalent isocyanate having 3 or morefunctionalities (F). In order to provide a sufficiently highpolymerization rate and minimize the coloring of the resulting lacticpolyester, the amount of the ring opening polymerization catalyst (D) isparticularly preferably from 0.01 to 0.1% by weight.

In the case where the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C) is reacted with thepolyester terminated by hydroxyl group at both ends (B1) or thepolyvalent carboxylic acid having 3 or more functionalities and/or acidanhydride thereof (C), the dicarboxylic acid and the diol are allowed toundergo dehydration reaction and deglycolation reaction to prepare apolyester, a catalyst is preferably used.

As the catalyst employable in the present invention there may be usedany catalyst generally known as an esterification catalyst. Examples ofsuch a catalyst include organic or inorganic compounds of at least onemetal selected from the group consisting of tin, zinc, lead, titanium,antimony, cerium, germanium, cobalt, manganese, iron, aluminum,magnesium, calcium and strontium. For example, metal alkoxides, organicacid salts of metal, chelates, metal oxides, etc. may be used.Particularly useful among these compounds is organic titanium compoundsuch as alkylester titanate, titanium oxy acetyl acetonate, and titaniumoxalate.

The added amount of the catalyst is preferably from 0.001 to 0.5% byweight based on 100% by weight of the sum of the polyvalent carboxylicacid having 3 or more functionalities and/or acid anhydride thereof (C),the dicarboxylic acid or acid anhydride thereof and the diol. In orderto provide a sufficiently high polymerization rate and minimize thecoloring of the resulting lactic polyester, the added amount of thecatalyst is particularly preferably from 0.01 to 0.1% by weight.

In the case where the polyvalent isocyanate having 2 or morefunctionalities (E) or the polyvalent isocyanate having 3 or morefunctionalities (F) is used, a catalyst is preferably used. As thecatalyst employable in the present invention there may be used anycatalyst generally known as an urethanation catalyst. Examples of suchan urethanation catalyst include organic or inorganic compounds of atleast one metal selected from the group consisting of tin, zinc, leadand titanium. For example, metal alkoxides, organic acid salts of metal,chelates, metal oxides, etc. may be used. Particularly useful amongthese compounds is organic tin compound such as dibutyltin dilaurate andtin octanoate.

Specific examples of the preparation process will be sequentiallydescribed hereinafter.

In the case where the lactide (A) and the polyester ((B1), (B2), (B3) or(B4)) are polymerized as essential components, the polymerizationtemperature is preferably from not lower than the melting point of thelactide to not higher than 185° C. in the light of the balance ofpolymerization. If the polymerization temperature falls within thisrange, the coloring of the lactic polyester due to the decompositionreaction can be inhibited. Since the melting point of the lactide isnear 100° C., the polymerization temperature is preferably from notlower than 100° C. to not higher than 185° C., more preferably from 145°C. to 180° C. in the light of the balance of polymerization. Thus, thelactic polyester can be prevented from the reduction of molecular weightor coloring due to decomposition reaction.

In the case where the lactide (A), the polyester terminated by hydroxylgroup at both ends (B1) and the polyvalent carboxylic acid having 3 ormore functionalities and/or acid anhydride thereof (C) are mixed at oncebefore polymerization, the mixture is heated and melted or stirred witha solvent, followed by the addition of the ring opening polymerizationcatalyst (D).

In this case, since the lactide (A), the polyester terminated byhydroxyl group at both ends (B1) and the polyvalent carboxylic acidhaving 3 or more functionalities and/or acid anhydride thereof (C) canbe subjected to polymerization at one time, rapid reaction is possibleand thus this process is particularly preferred from the standpoint ofproduction property.

In the case where the lactide (A) and the polyester terminated byhydroxyl group at both ends (B1) are allowed to undergo ring openingcopolymerization in the presence of a ring opening polymerizationcatalyst (D) to prepare a high molecular lactic copolymer polyesterhaving a weight-average molecular weight of from 10,000 to 300,000 whichis then reacted with the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C), the mixture of thelactide (A) and the polyester (B1) is heated and melted or stirred inthe presence of a solvent, followed by the addition of the ring openingpolymerization catalyst (D).

The reaction of the high molecular lactic copolymer polyester with thepolyvalent carboxylic acid having 3 or more functionalities and/or acidanhydride thereof (C) is, when the polymerization is effected in theabsence of solvent, conducted at a temperature of from 100° C. to 210°C. for from 10 to 180 minutes with stirring. In this case, the reactioncan be advantageously effected under reduced pressure to provide ahigher reaction rate. On the other hand, in the case where thepolymerization is effected in the presence of a solvent, thepolymerization is preferably effected at a temperature of from 80° C. to210° C. for from 10 to 180 minutes. The reaction may be effectedoptionally in the presence of a catalyst.

The foregoing process differs from the process which comprises thereaction of a condensed polyester of a hydroxycarboxylic acid such aspolylactic acid with a polyvalent carboxylic acid and/or acid anhydridethereof. In the process of the present invention, the polyester to bereacted with the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C) is terminated byhydroxyl group at both ends. Thus, many reactive end groups can takepart in the reaction. Therefore, all the polymer chains can beadvantageously connected to each other.

In the case where the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C) is reacted with thepolyester terminated by hydroxyl group at both ends (B1), followed bythe copolymerization with the lactide (A), the polyester terminated byhydroxyl group at both ends (B1) is prepared, and the polyvalentcarboxylic acid having 3 or more functionalities and/or acid anhydridethereof (C) is then heated and melted with the polyester (B1) or mixedwith the polyester (B1) in the presence of a solvent, optionallyfollowed by the addition of a catalyst, before reaction.

In the case where the polymerization is effected in the absence ofsolvent, the polymerization is effected at a temperature of from 100° C.to 210° C. for from 10 to 180 minutes with stirring. In this case, thereaction can be advantageously effected under reduced pressure toprovide a higher reaction rate. In the case where the polymerization iseffected in the presence of a solvent, the polymerization is preferablyeffected at a temperature of from 80° C. to 210° C. for from 10 to 180minutes. In the case where the polymerization product and the polyesterterminated by hydroxyl group at both ends (B2) obtained by the reactionof the lactide (A) with the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C) are mixed forpolymerization, the mixture is heated and melted or stirred with asolvent, followed by the addition of the ring opening polymerizationcatalyst (D).

In accordance with the foregoing process, when the polymerizationproduct is polymerized with the polyester terminated by hydroxyl groupat both ends obtained by the reaction of the lactide with the polyvalentcarboxylic acid having 3 or more functionalities and/or acid anhydridethereof, an ester exchange reaction occurs to obtain a homogeneouscopolymer.

In the case where the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride (C) is allowed to undergodehydration reaction and deglycolation reaction with the dicarboxylicacid and the diol, followed by the copolymerization with the lactide(A), the dehydration reaction of the polyvalent carboxylic acid having 3or more functionalities and/or acid anhydride thereof (C) with thedicarboxylic acid and the diol is preferably effected at a temperatureof from 160° C. to 250° C. for from 5 to 16 hours in an atmosphere ofinert gas.

The deglycolation reaction is effected under a reduced pressure of nothigher than 5 Torr at a temperature of from 170° C. to 260° C. for from2 to 16 hours. The polyester terminated by hydroxyl group at both ends(B3) thus obtained and the lactide (A) are heated and melted or mixed inthe presence of a solvent, followed by the addition of the ring openingpolymerization catalyst (D).

In the case where the polyvalent isocyanate having 2 or morefunctionalities (E) is reacted with the polyester terminated by hydroxylgroup at both ends (B1), followed by the copolymerization with thelactide (A), the polyvalent isocyanate having 2 or more functionalities(E) is heated and melted with the polyester terminated by hydroxyl groupat both ends (B1) or mixed with the polyester (B1) in the presence of asolvent, optionally followed by the addition of a catalyst, before thepreparation of the polyester (B4).

The foregoing reaction is preferably effected at a temperature of from80° C. to 210° C. for from 10 to 180 minutes with stirring. In the casewhere the lactide (A) and the polyester (B4) are mixed forpolymerization, the mixture is heated and melted or stirred in thepresence of a solvent, followed by the addition of a ring openingpolymerization catalyst (D). In this process, when the lactide and thepolyester (B4) are mixed, an ester exchange reaction occurs to obtain ahomogeneous copolymer.

In the case where the lactide (A) and the polyester terminated byhydroxyl group at both ends (B1) are allowed to undergo ring openingcopolymerization in the presence of a ring opening polymerizationcatalyst (D) to prepare a high molecular lactic copolymer polyesterhaving a weight-average molecular weight of from 10,000 to 300,000 whichis then reacted with the polyvalent isocyanate having 3 or morefunctionalities (F), the mixture of the lactide (A) and the polyester(B1) is heated and melted or stirred in the presence of a solvent,followed by the addition of the ring opening polymerization catalyst(D).

The reaction of the high molecular lactic copolymer polyester with thepolyvalent isocyanate having 3 or more functionalities (F) follows theheating and melting of the mixture of the polymerization product withthe polyvalent isocyanate (F) or the stirring of the mixture in thepresence of a solvent. The reaction is preferably effected at atemperature of from 80° C. to 210° C. for from 10 to 180 minutes. Thereaction may be effected optionally in the presence of a catalyst.

The foregoing process differs from the process which comprises thereaction of a condensed polyester of a hydroxycarboxylic acid such aspolylactic acid with a polyvalent carboxylic acid and/or acid anhydridethereof. In the process of the present invention, the polyester to bereacted with the polyvalent isocyanate having 3 or more functionalities(F) is terminated by hydroxyl group at both ends. Thus, many reactiveend groups can take part in the reaction. Therefore, all the polymerchains can be advantageously connected to each other.

The high molecular lactic copolymer polyester obtained by the foregoingpreparation process has a weight-average molecular weight of from 20,000to 600,000 to maintain its formability or moldability and the strengthor flexibility of the formed or molded product. Taking into account thereduction of the molecular weight during formation, the high molecularlactic copolymer polyester preferably has a weight-average molecularweight of from 50,000 to 600,000.

In order to prevent the decomposition and coloring of the lactide, theoptimum atmosphere in which the polymerization thereof and the reactionthereof with the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C), the polyvalentisocyanate having 2 or more functionalities (E) or the polyvalentisocyanate having 3 or more functionalities (F) can occur is a driedinert gas. In particular, the reaction is preferably effected in anatmosphere of nitrogen or argon gas or with such an inert gas bubbledthereinto. At the same time, the polyester terminated by hydroxyl groupat both ends ((B1), (B2), (B3) or (B4)) or mixture thereof as a startingmaterial is preferably dehydrated and dried before use.

Since the lactide is soluble in a solvent, it can be polymerized in thepresence of a solvent. Examples of the solvent employable herein includebenzene, toluene, ethylbenzene, xylene, cyclohexanone, methyl ethylketone, and isopropyl ether.

The high molecular lactic copolymer polyester of the present inventioncan be prepared by means of an ordinary polymerization vessel. However,since the viscosity of the polyester is raised as the molecular weightof the polyester is increased, the copolymerization reaction in such anordinary polymerization vessel is liable to the inhibition of agitationthat causes local heating resulting in local denaturation. Further, whenthe copolymerization product is withdrawn from the polymerizationvessel, the product can be attached to the wall of the vessel or theagitating blade, causing the drop of yield. The yield and productivitycan be enhanced by employing a continuous preparation process.

In an example of the continuous preparation process, a series connectionof two or more agitated reaction vessels which can vary in the manner ofagitation with the progress of reaction and thus can provide anefficient temperature control is preferably used since the startingmaterials of the high molecular lactic copolymer polyester of thepresent invention have a low viscosity and the resulting polymer resinwhich shows a vigorous change in the viscosity to as high as over 10,000poise and is liable to thermal decomposition finds extremely greatdifficulty in temperature control.

In the foregoing continuous polymerization process employing a seriesconnection of two or more agitated reaction vessels, a plurality ofagitated reaction vessels are connected in series. In operation, thepolymerization reaction is allowed to proceed to a certain extent in thefirst reaction vessel. The resulting product is transferred to thesubsequent reaction vessel where it is then further allowed to undergoreaction. If necessary, the resulting product is then transferred to thesubsequent reaction vessel for further reaction. In this process, it islikely that the starting materials can be mixed into the product inunreacted form. In order to solve this problem, the number of reactionvessels is preferably increased.

The agitated reaction vessel as defined herein is a dynamic mixerequipped with an agitator. More particularly, it is a reaction vesselequipped with an agitator having agitating blades connected to a powermachine.

Referring to the shape of the agitating blade in the agitated reactionvessel used in the continuous reaction process employing a multiple ofreaction vessels, agitation can be fairly effected regardless of theshape of the agitating blade in the reaction vessel used in the initialstage of reaction because the resulting viscosity is low. However, aturbine blade, a Pfaudler type impeller, a helical ribbon blade or amulti-stage blade consisting of these blades is preferably used for thepurpose of efficiently producing upward and downward flows in thereaction vessel.

A blade which can homogeneously agitate the entire reaction system suchas anchor blade is preferred. A high viscosity is developed in thereaction vessels used in the middle stage and final stage of thereaction. Thus, the shape of the agitating blade has a great effect onthe agitating effect. Agitation can be hardly effected particularly inthe vicinity of the wall of the reaction vessel. For the purpose ofefficiently scratch the reaction product off the wall of the reactionvessel, a blade which can homogeneously agitate the entire reactionsystem such as turbine blade, helical ribbon blade and anchor blade ispreferred.

In the case where starting materials are supplied into the reactionsystem while withdrawing the same amount of the reaction product, themore the total number of reaction vessels is, the less is the amount ofunreacted starting materials to be mixed into the reaction product.Further, the required capacity of the reaction vessel is reduced,lowering the required agitating power in each reaction vessel and hencefacilitating the temperature control with a heating medium. However, themore the number of reaction vessels is, the more is the required numberof power machines, and the more is the required number of pumpsconnecting reaction vessels. Thus, the control is more complicated.

Since the complication of the apparatus is economically disadvantageous,the number of agitated reaction vessels used should be predetermined assmall as possible so far as a sufficient agitating effect can beexerted. If the capacity of the reaction vessel is excessive as comparedwith the supplied amount of the starting materials, it is thought thattwo or more reaction vessels suffice. However, such an excessivecapacity of the reaction vessel as compared with the supplied amount ofthe starting materials is economically disadvantageous, and it isthought that the required number of reaction vessels is 3 or more.Further, the complication of the apparatus caused by the increase in thenumber of reaction vessels is not desirable from the standpoint ofoperation and economy, and the number of reaction vessels is preferablyfrom 3 to 5.

An example of agitated reaction vessel is a latent heat cooling typeagitated reaction vessel. This is a reaction vessel which can utilizethe heat of vaporization of the monomer as starting material or solventto control the reaction temperature. When the starting material ischarged into the reaction vessel, a space is produced at the top of thereaction vessel. The heat dispersion caused by the evaporation from theliquid surface to the space makes cooling possible. Thus, thetemperature control is easily made, making it possible to predeterminethe reaction temperature to a high value and hence realize a highproductivity. A condenser for catching the monomer and/or solvent isprovided at the top of the reaction vessel.

In this arrangement, the transfer of the solution from one reactionvessel to the subsequent reaction vessel requires a pump every vessel.The starting material is supplied into a first agitated reaction vesselby means of a pump. The reaction solution is then transferred from thefirst vessel to a second vessel by means of another pump. The reactionsolution is then transferred from the second vessel to a third vessel bymeans of another pump, and so on.

Another example of the agitated reaction vessel is a filling typeagitated reaction vessel. This is an apparatus comprising a seriesconnection of a multiple of reaction vessels between which the reactionsolution is transferred by means of a single pump. A single pump may beused to feed the starting material into the reaction vessels. Further,the reaction can be effected in a closed system. Thus, the charging ofstarting material, reaction, degasification and polymer pelletizationcan be effected without coming into contact with the externalatmosphere. This is an advantage which cannot be obtained by theconventional batch type reaction vessel. Thus, this is a continuouspolymerization process extremely suitable for the preparation of adecomposable polymer of the present invention which can be decomposed byheat, oxygen or water content.

As another example of the continuous production process there ispreferably used one employing a static mixer.

The term "static mixer" as used herein is meant to indicate a staticmixing machine free of mobile portion, i.e., agitator, as opposed tomixing machine equipped with agitator. More particularly, it is a mixerequipped with a mobile portion-free mixing element fixed in a pipe. Themixing element is adapted to split the flow and change or invert thedirection of flow. Thus, the flow is divided axially or crosswise, andits direction is then changed or inverted. This procedure is repeated tomix the solution. Some static mixers are equipped with a jacket ataround the pipe for heat exchange. In some static mixers, the mixingelement is equipped with a heat exchange tube through which a heatingmedium passes.

The static mixer is generally tubular. It comprises a linear connectionof a plurality of static mixers. In operation, the starting material iscontinuously supplied through an intake in an atmosphere of inert gas sothat the resulting polymer continuously moves in the static mixer. Inthis manner, the operation can be continuously effected without cominginto contact with the external atmosphere through the procedureconsisting of the charging of starting material, polymerization,degasification, and polymer pelletization.

In the preparation of the high molecular lactic copolymer polyester ofthe present invention, the polymerization apparatus equipped with astatic mixer can be singly used to effect all polymerization reactions.However, the static mixer can be arranged such that polymerization iseffected by a polymerization vessel equipped with an ordinary agitatorin the initial stage of polymerization where a relatively low polymerviscosity is developed while polymerization is effected by apolymerization apparatus equipped with a static mixer in the latterstage of polymerization where a high polymer viscosity is developed toexert a remarkable agitating effect particularly in the latter stage ofpolymerization where a high polymer viscosity is developed. Therefore, acontinuous polymerization apparatus comprising a static mixer connectedto an agitated polymerization vessel may be used.

The lactide, the polyester polymer and the resulting high molecularpolyester can be easily solved in solvents. Therefore, polymerizationcan be effected with a solvent. The resulting high molecular lacticpolyester exhibits a high melting point and a high melt viscosity andthus can hardly be polymerized. However, when provided with a solvent,the polymerization system exhibits a reduced viscosity and thus can beeasily stirred and hence polymerized.

In particular, the use of the continuous polymerization apparatusequipped with a static mixer requires a reduced extrusion pressure ofthe polymerization solution or can simplify the arrangement of apolymerization apparatus equipped with an internal device for heatingmedium for the purpose of controlling temperature or a turning blade forthe purposed of agitation.

Further, since the foregoing continuous polymerization apparatus canprovide easy agitation, the temperature control can be easily effected,uniformalizing temperature therein. Thus, a less colored lacticpolyester can be obtained.

For the reaction with the polyvalent carboxylic acid having 3 or morefunctionalities and/or acid anhydride thereof (C) or the polyvalentisocyanate (E) or (F), a line may be provided such a manner that thereaction component (C), (E) or (F) is added at its proper addition time.

Preferred examples of the solvent employable herein include benzene,toluene, ethylbenzene, xylene, cyclohexanone, methyl ethyl ketone,methyl isobutyl ketone, and isopropyl ether. If the polymerization iseffected with such a solvent, the polymerization rate is lowered. Forthe purpose of overcoming this difficulty, the polymerizationtemperature is preferably from 140° C. to 195° C.

The polymerization or reaction with the polyvalent carboxylic acidhaving 3 or more functionalities and/or acid anhydride thereof (C) orpolyvalent isocyanate ((E) or (F)) can be inhibited by water content.Further, a decomposition reaction is accelerated. Thus, thepolymerization or reaction is preferably effected in an atmosphere ofdried inert gas. In particular, the polymerization or reaction ispreferably effected in an atmosphere of nitrogen or argon gas or in astream of inert gas.

For the purpose of removing the lactide, solvent and malodoroussubstances remaining in the latter stage of polymerization,degasification is preferably effected under reduced pressure. Thegasification process can reduce the content of remaining lactide, makingit possible to remarkably enhance the storage stability of the resultinghigh molecular lactic polyester.

The remaining lactide causes some troubles on the high molecular lacticpolymer in sheet form. For example, the remaining lactide causes watercontent to be attached to the sheet. The water content thus attachedcauses the hydrolysis of the sheet. Further, the remaining lactidecauses the sheet to be fused due to heat. Moreover, the remaininglactide can sublimate and scatter from the film sheet made of the highmolecular lactic polymer. Therefore, the content of the remaininglactide in the high molecular lactic polyester of the present inventionis preferably not more than 2% by weight, more preferably not more than1% by weight.

In some detail, degasification is preferably effected by withdrawing theresulting polymer while being heated under reduced pressure. In order toinhibit the reduction of the molecular weight of the high molecularlactic polyester, degasification is preferably effected at a temperatureof from 145° C. to 230° C. for from 2 to 30 minutes under a pressure offrom 0.1 to 200 Torr. Alternatively, degasification may be effected bypelletizing or grinding the high molecular lactic polyester thuspolymerized, and then withdrawing the polyester while being heated underreduced pressure.

In order to inhibit the reduction of the molecular weight of the highmolecular lactic polyester, degasification is preferably effected at atemperature of from 60° to 200° C. under a pressure of from 0.1 to 50Torr for from 2 to 400 minutes. This gasification process can reduce thecontent of the remaining lactide, which is normally about 2.5%, to notmore than 1.0%, even to not more than 0.1% as necessary.

During the preparation of the copolymer of the present invention, cyclicesters other than the lactide (A) may be added to prepare a highmolecular lactic polyester. In particular, a lactone may be added in anamount of from 1 to 20% by weight for the purpose of softening theresulting polyester.

The cyclic esters to be added other than the lactide are notspecifically limited. Specific examples of these cyclic esters includecyclic dimers of hydroxy acid such as glycolide, and inner lactides suchas ε-caprolactone, γ-valerolactone and γ-undecalactone. The more thecontent of lactone is, the lower is the glass transition point and themelting point of the resulting polyester, and the higher is theflexibility thereof.

The preparation process of the present invention can provide productsranging from a high molecular lactic polyester having a high rigidity toa high molecular lactic polyester having a high flexibility. Examples ofthese products include polymers useful as general-purpose resins havingdecomposability and a tensile elasticity modulus of from 500 to 50,000kg/cm², such as resin for wrapping material (e.g., sheet, film),foamable resin, extrudable resin, injection-moldable resin, ink resinand laminating resin. The preparation process of the present inventionis particularly useful for the preparation of polymers for wrappingmaterial.

The lactic copolymer polyester of the present invention can be easilyextruded by T-die casting or tubular film process so that it is formedinto sheet or film. Since the lactic copolymer polyester has a highhygroscopicity and thus is liable to hydrolysis, it can be easily formedinto a wrapping material such as sheet or film by means of an ordinarysingle-screw extruder. However, the water content should be carefullycontrolled.

As the screw to be used in the extruder there may be used an ordinaryfull-frighted screw having L/D of from about 20 to 30. The screw may beoptionally vented. In the case where a single-screw extruder is used,dehumidification is preferably effected by a vacuum dryer or the like sothat the water content in the starting material is controlled to notmore than 50 ppm to avoid hydrolysis in the extruder. The optimumextrusion temperature depends on the molecular weight of the lacticcopolymer polyester used and the amount of remaining lactide but ispreferably not lower than the flow initiation temperature.

In the T-die casting process, the sheet or film thus extruded isnormally cooled over a temperature-controlled mirror-like surface ortextured roll. In this process, an air knife may be used. Further, if avented two-screw extruder is used, a high dehydration effect can beexerted, eliminating the necessity for pre-drying and hence enabling anefficient film formation. The tubular film process can be easilyeffected by means of an ordinary forming apparatus equipped with acircular die or air ring. There is no need of special accessoryapparatus. In order to provide a uniform section, the die, air ring orwinder may be rotated.

The sheet or film thus formed may be monoaxially or biaxially orientedat a temperature of from not lower than the glass transition temperaturethereof to not higher than the melting point thereof by a tenteringmethod or tubular film process. The sheet or film thus oriented can beprovided with molecular orientation that improves the physicalproperties such as impact resistance, rigidity and transparency thereof.

The orientation may be effected simultaneously or successively. Theorientation speed is not specifically limited. The stretch ratio is notspecifically limited. In the case of biaxial orientation, the optimumstretch ratio is normally from 2 to 4 in both lengthwise direction andcrosswise direction. For films which need to be shrinked upon heatingsuch as shrink film, a stretch ratio as high as from 3 to 6 is desirablein one direction or two directions. In order to enhance the heatresistance of the sheet or film, the sheet or film which has beenoriented may be subjected to heat setting for the removal of stress oracceleration of crystallization.

During the formation of sheet or film, an ordinary filler such asinorganic filler (e.g., talc, calcium carbonate, silica, clay,diatomaceous earth, perlite) and organic filler (e.g., woodmeal) may beincorporated in the material. Further, an oxidation inhibitor such as2,6-di-t-butyl-4-methylphenol (BHT) and butyl hydroxyanisole (BHA), anultraviolet absorbent such as salicylic acid derivative, benzophenoneand benzotriazole or a stabilizer such as phosphoric ester andcarbodiimide may be used to enhance the thermal stability duringformation.

The added amount of such a stabilizer is not specifically limited but ispreferably from 0.01 to 1% based on the weight of the high molecularlactic polyester. The high molecular lactic polyester of the presentinvention exhibit a sufficient plasticity as it is and thus exhibits agood melt-formability. In order to accelerate the softening of theproduct, a plasticizer such as dioctyl adipate, dioctyl sebacate,trioctyl trimellitate, diethyl phthalate, dioctyl phthalate,polypropyleneglycoladipic acid and butanediol adipate may be added tothe material.

Among these plasticizers, the polyester adipate plasticizer is desirablefrom the standpoint of formability or moldability and flexibility. Inparticular, a polyester adipate having a weight-average molecular weightof not more than 20,000 with its ends blocked by alcohol has a goodcompatibility with the polymer and thus is particularly desirable.

The added amount of such a plasticizer is not specifically limited. Inorder to avoid the elution of excessive plasticizer from the resin,i.e., bleeding, the added amount of such a plasticizer is preferablyfrom 1 to 30% based on the weight of the high molecular lacticpolyester.

Further, a metallic soap such as zinc stearate, magnesium stearate andcalcium stearate, a lubricant such as mineral oil, liquid paraffin andethylenebisstearamide, a nonionic surface active agent such asglycerinaliphatic ester and sucrose aliphate, an ionic surface activeagent such as alkylsulfonic acid salt, a coloring agent such as titaniumoxide and carbon black, etc. may be added to the material.

A foamed product can be prepared by the addition of an inorganic foamingagent such as sodium bicarbonate and ammonium bicarbonate or an organicfoaming agent such as azodicarbonamide, azobisisobutyronitrile andsulfonylhydrazide or by previously impregnating the polymer of thepresent invention with a foaming agent such as pentane, butane and Freonor by directly supplying such a foaming agent into the extruder duringextrusion. The polyester of the present invention can be laminated witha paper, aluminum foil or other decomposable polymer films by extrusionlamination method, dry lamination method or coextrusion method.

The fabrication of the sheet thus formed can be accomplished by vacuumforming, pressure forming, vacuum pressure forming or the like. Theformation of the lactic copolymer polyester of the present inventioninto sheet can be accomplished by means of a known apparatus for use inthe preparation of sheet made of general-purpose resin.

In the vacuum forming or vacuum pressure forming, plug-assist formingmay be effected. The oriented sheet may be subjected to pressureforming. During the forming, the mold may be optionally heated orcooled. In particular, the mold can be heated to a temperature of notlower than the crystallization temperature to positively promotecrystallization, making it possible to improve the heat resistance ofthe product.

The fabrication of the film thus formed can be accomplished by anordinary fabrication method. In some detail, the film can be heat-sealedby means of an ordinary bag making machine such as horizontal pillowtype bag making machine, horizontal pillow type bag making machine andtwist bag making machine to obtain a bag-shaped product. In order toobtain a formed product other than sheet and film, an ordinary injectionmolding machine can be used to obtain a molded product such as vessel.The polyester of the present invention can also be easily blow-molded.In some detail, a single-layer or multi-layer bottle can be easilyformed by the use of an existing blow molding machine. Referring topress molding, there is no special problem. In some detail, an ordinarypress molding machine can be used to obtain a single-layer or laminatedproduct.

The high molecular lactic polyester obtained according to the presentinvention has a good biodegradability. Even if discarded after used asgeneral-purpose resin or wrapping material or rejected and discardedfrom the production line, it can help reduce the amount of wastes. Inparticular, even if discarded into the sea, it is hydrolyzed ordecomposed by microorganism. When decomposed under the seawater, thepolyester of the present invention can show a deteriorated resinstrength in several months and thus can be decomposed to an extent suchthat the initial appearance is not maintained.

The present invention will be further described in the followingexamples and comparative examples, but the present invention should notbe construed as being limited thereto. The "parts" as used herein is byweight unless otherwise specified.

The molecular weight was measured by a GPC measuring apparatus(hereinafter referred to as "GPC"; column temperature: 40° C.; solvent:tetrahydrofuran) relative to polystyrene as a reference sample.

The glass transition point and melting point were measured by means ofdifferential scanning calorimeter (hereinafter referred to as "DSC").The percent heat loss was measured by a differential thermogravimetricanalyzer (hereinafter referred to as "TG/DTA" (The sample was heated ata rate of 100° C./min. from 20° C. to 220° C. wherein it was then keptfor 50 minutes)).

For the tensile test, a 200-μm thick film which had been prepared bysubjecting the polyester to processing by a hot press at a temperatureof from 160° C. to 170° C. under a pressure of 200 kg/cm² for 2 minuteswas subjected to test by a tensile testing machine (rate of pulling: 20mm/min.). The Vicat softening temperature test was conducted inaccordance with A method of JIS K7206. As the test specimen there wasused a dumbbell-shaped piece formed by a 1-ounce injection moldingmachine. The machines as mentioned above are as follows:

    ______________________________________                                        GPC:    TOSOH HLC-8020 (available from TOSOH                                          CORPORATION)                                                          DSC:    DSC 200 (available from Seiko Instruments,                                    Inc.)                                                                 TG/DTA: TG/DTA 220 (available from Seiko Instruments,                                 Inc.)                                                                 Tensile testing machine:                                                                     Tensilon (available from                                                      Toyo Seiki K.K.)                                               Vicat softening temperature:                                                                   HDT. VSPT. TESTER                                                             (available from Toyo                                                          Seiki K.K.)                                                  ______________________________________                                    

In the following examples, any one of the following three polyesters wasused for examination unless otherwise specified.

As the polyester comprising an aliphatic dicarboxylic acid componentthere was used a polyester comprising 50 mol % of an adipic acidcomponent, 28 mol % of an ethylene glycol component and 22 mol % of aneopentyl glycol component, having a weight-average molecular weight of30,210 and a number-average molecular weight of 15,200. This polyesterwill be hereinafter referred to as "(P-1)".

As the polyester comprising an aromatic dicarboxylic acid component andan aliphatic dicarboxylic acid component there was used a polyestercomprising 14 mol % of a terephthalic acid component, 16 mol % of anisophthalic acid component, 20 mol % of an adipic acid component, 28 mol% of an ethylene glycol component and 22 mol % of a neopentyl glycolcomponent, having a weight-average molecular weight of 45,200 and anumber-average molecular weight of 24,700. This polyester will behereinafter referred to as "(P-2)".

The third polyester will be described later.

EXAMPLE 1

(P-1) in an amount of 10 parts, L-lactide in an amount of 90 parts, andpyromellitic anhydride in an amount of 0.002 part based on 100 parts ofthe sum of the amount of L-lactide and (P-1) were mixed. Thesecomponents were dissolved and mixed at a temperature of 175° C. for 0.5hour in an atmosphere of nitrogen gas. To the reaction mixture was thenadded 0.02 part of tin octanoate as a ring opening polymerizationcatalyst.

The reaction mixture was then allowed to undergo reaction at atemperature of 175° C. for 3 hours. The resulting copolymer was thenwithdrawn. The high molecular lactic polyester thus obtained was ayellowish transparent resin. It was confirmed from the result of GPCthat a high molecular lactic polyester had been produced having aweight-average molecular weight of 315,000 and a number-averagemolecular weight of 122,000, which are greater than that of thepolyester comprising an aromatic dicarboxylic acid component and analiphatic dicarboxylic acid component as starting materials.

The result of GPC effected 3 hours after reaction shows that thefraction derived from the copolymer is single, demonstrating theproduction of a single copolymer. A small fraction derived from theremaining lactide was confirmed. It was also found that the highmolecular lactic polyester has a glass transition point of about 56° C.and a melting point of about 158° C. The high molecular lactic polyesterexhibited a tensile break stress of 41%, a tensile break strength of 520kgf/cm² and an initial tensile elasticity modulus of 10,100 kgf/cm².

EXAMPLE 2

(P-2) in an amount of 5 parts, L-lactide in an amount of 93 parts,D-lactide in an amount of 2 parts, pyromellitic anhydride in an amountof 0.05 part based on 100 parts of the sum of the amount of the lactideand (P-2), and toluene in an amount of 20 parts were mixed. Thesecomponents were then dissolved and mixed at a temperature of 175° C. inan atmosphere of nitrogen gas for 0.5 hour. To the reaction mixture werethen added 0.02 part of tin octanoate as a ring opening polymerizationcatalyst. The reaction mixture was allowed to undergo reaction at atemperature of 175° C. for 3 hours. After reaction, toluene was removedunder reduced pressure.

The high molecular lactic polyester thus produced was a colorlesstransparent resin having a weight-average molecular weight of 356,000and a number-average, molecular weight of 152,000. The high molecularlactic polyester exhibited a glass transition point of about 58° C., amelting point of about 160° C., a tensile break stress of 9.6%, atensile break strength of 650 kgf/cm² and an initial tensile elasticitymodulus of 13,000 kgf/cm².

EXAMPLE 3

(P-1) in an amount of 30 parts, L-lactide in an amount of 68 parts,D-lactide in an amount of 2 parts, trimellitic anhydride in an amount of1 part based on 100 parts of the sum of the amount of the lactide and(P-1), and toluene in an amount of 15 parts were mixed. These componentswere then dissolved and mixed at a temperature of 165° C. in anatmosphere of nitrogen gas for 0.5 hour. To the reaction mixture werethen added 0.02 part of tin octanoate as a ring opening polymerizationcatalyst. The reaction mixture was allowed to undergo reaction at atemperature of 165° C. for 3 hours. After reaction, toluene was removedunder reduced pressure.

The high molecular lactic polyester thus produced was a colorlesstransparent resin having a weight-average molecular weight of 110,000and a number-average molecular weight of 42,000. The high molecularlactic polyester exhibited a glass transition point of about 53° C., amelting point of about 150° C., a tensile break stress of 230%, atensile break strength of 490 kgf/cm² and an initial tensile elasticitymodulus of 8,100 kgf/cm².

EXAMPLE 4

(P-2) in an amount of 5 parts, L-lactide in an amount of 93 parts,D-lactide in an amount of 2 parts, and toluene in an amount of 15 partswere mixed. These components were then dissolved and mixed at atemperature of 175° C. in an atmosphere of nitrogen gas for 0.5 hour. Tothe reaction mixture were then added 0.02 part of tin octanoate as aring opening polymerization catalyst. The reaction mixture was allowedto undergo polymerization for 3 hours. The lactic copolymer polyesterthus obtained had a weight-average molecular weight of 161,000. To thelactic copolymer polyester was then added pyromellitic anhydride in anamount of 0.002 part based on 100 parts of the sum of the amount of thelactide and (P-2). The reaction mixture was then allowed to undergoreaction for 3 hours. After reaction, toluene was removed under reducedpressure.

The high molecular lactic polyester thus produced was a colorlesstransparent resin having a weight-average molecular weight of 517,000and a number-average molecular weight of 215,000. The high molecularlactic polyester exhibited a glass transition point of about 59° C., amelting point of about 158° C., a tensile break stress of 12%, a tensilebreak strength of 550 kgf/cm² and an initial tensile elasticity modulusof 11,900 kgf/cm².

EXAMPLE 5

(P-1) in an amount of 30 parts, L-lactide in an amount of 70 parts, andtoluene in an amount of 15 parts were mixed. These components were thendissolved and mixed at a temperature of 165° C. in an atmosphere ofnitrogen gas for 0.5 hour. To the reaction mixture were then added 0.03part of tin octanoate as a ring opening polymerization catalyst. Thereaction mixture was allowed to undergo polymerization for 3 hours. Thelactic copolymer polyester thus obtained had a weight-average molecularweight of 73,000. To the lactic copolymer polyester was then addedpyromellitic anhydride in an amount of 0.05 part based on 100 parts ofthe sum of the amount of the lactide and (P-1). The reaction mixture wasthen allowed to undergo reaction for 2 hours.

After reaction, toluene was removed under reduced pressure. The highmolecular lactic polyester thus produced was a colorless transparentresin having a weight-average molecular weight of 145,000 and anumber-average molecular weight of 70,100. The high molecular lacticpolyester exhibited a glass transition point of about 54° C., a meltingpoint of about 149° C., a tensile break stress of 330%, a tensile breakstrength of 470 kgf/cm² and an initial tensile elasticity modulus of8,200 kgf/cm².

EXAMPLE 6

(P-1) in an amount of 5 parts, L-lactide in an amount of 93 parts,D-lactide in an amount of 2 parts, and toluene in an amount of 20 partswere mixed. These components were then dissolved and mixed at atemperature of 165° C. in an atmosphere of nitrogen gas for 0.5 hour. Tothe reaction mixture were then added 0.05 part of tin octanoate as aring opening polymerization catalyst. The reaction mixture was allowedto undergo polymerization for 3 hours. The lactic copolymer polyesterthus obtained had a weight-average molecular weight of 161,000. To thelactic copolymer polyester was then added pyromellitic anhydride in anamount of 0.5 part based on 100 parts of the sum of the amount of thelactide and (P-1). The reaction mixture was then allowed to undergoreaction for 2 hours. After reaction, toluene was removed under reducedpressure.

The high molecular lactic polyester thus produced was a colorlesstransparent resin having a weight-average molecular weight of 327,000and a number-average molecular weight of 119,000. The high molecularlactic polyester exhibited a glass transition point of about 57° C., amelting point of about 156° C., a tensile break stress of 18%, a tensilebreak strength of 510 kgf/cm² and an initial tensile elasticity modulusof 13,000 kgf/cm².

EXAMPLE 7

(P-1) in an amount of 20 parts and toluene in an amount of 15 parts weremixed. These components were then dissolved and mixed at a temperatureof 100° C. in an atmosphere of nitrogen gas for 0.5 hour. To thereaction mixture were then added trimellitic anhydride in an amount of0.002 part based on 100 parts of (P-1) and tetraisopropyl titanate as acatalyst in an amount of 0.005 part. The reaction mixture was thenallowed to undergo reaction at a temperature of 120° C. for 2 hours. Thepolyester thus obtained exhibited a weight-average molecular weight of54,100 and a number-average molecular weight of 19,400.

To the polyester were then added L-lactide in an amount of 70 parts,D-lactide in an amount of 10 parts and tin octanoate as a ring openingpolymerization catalyst in an amount of 0.02 part. The reaction mixturewas then allowed to undergo reaction at a temperature of 175° C. for 3hours. After reaction, toluene was removed under reduced pressure. Thehigh molecular lactic polyester thus produced was a brownish transparentresin having a weight-average molecular weight of 168,000 and anumber-average molecular weight of 55,200.

The high molecular lactic polyester exhibited a glass transition pointof about 51° C., a melting point of about 154° C., a tensile breakstress of 180%, a tensile break strength of 420 kgf/cm² and an initialtensile elasticity modulus of 7,900 kgf/cm².

EXAMPLE 8

(P-2) in an amount of 5 parts and toluene in an amount of 15 parts weremixed. These components were then dissolved and mixed at a temperatureof 120° C. in an atmosphere of nitrogen gas for 0.5 hour. To thereaction mixture were then added pyromellitic anhydride in an amount of0.05 part based on 100 parts of (P-2) and tin octanoate as a catalyst inan amount of 0.001 part. The reaction mixture was then allowed toundergo reaction at a temperature of 120° C. for 2 hours. The polyesterthus obtained exhibited a weight-average molecular weight of 71,100 anda number-average molecular weight of 32,400.

To the polyester were then added L-lactide in an amount of 93 parts,D-lactide in an amount of 2 parts and tin octanoate as a ring openingpolymerization catalyst in an amount of 0.02 part. The reaction mixturewas then allowed to undergo reaction at a temperature of 175° C. for 3hours. After reaction, toluene was removed under reduced pressure. Thehigh molecular lactic polyester thus produced was a colorlesstransparent resin having a weight-average molecular weight of 325,000and a number-average molecular weight of 149,000. The high molecularlactic polyester exhibited a glass transition point of about 56° C., amelting point of about 152° C., a tensile break stress of 27%, a tensilebreak strength of 560 kgf/cm² and an initial tensile elasticity modulusof 12,000 kgf/cm².

EXAMPLE 9

31 mol % of a terephthalic acid component, 17 mol % of an adipic acidcomponent, 23 mol % of an ethylene glycol component, 27 mol % of aneopentyl glycol component and 0.05 mol % of a pyromellitic anhydridecomponent were charged. The reaction mixture was then esterified at atemperature of from 205° C. to 210° C. to have an acid value of 8.1. Tothe reaction mixture was then added 100 ppm of tetraisopropyl titanate.The reaction mixture was then allowed to undergo reaction at atemperature of from 215° C. to 220° C. Eventually, the reaction mixturewas allowed to undergo deglycolation reaction under a pressure of 0.5Torr for 8 hours.

The aromatic aliphatic polyester thus obtained exhibited aweight-average molecular weight of 118,000 and a number-averagemolecular weight of 34,500 (hereinafter referred to as "(P-3)"). To 10parts of the polyester thus obtained were then added 90 parts ofL-lactide and 15 parts of toluene. These components were was thendissolved and mixed at a temperature of 175° C. in an atmosphere ofnitrogen gas for 0.25 hour. To the reaction mixture were then added 0.02part of tin octanoate as a ring opening polymerization catalyst. Thereaction mixture was then allowed to undergo reaction for 3 hours. Tothe reaction mixture was then added 0.1 part of ε-caprolactone. Thereaction mixture was then allowed to undergo reaction at a temperatureof 175° C. for 1 hour. After reaction, toluene was removed under reducedpressure.

The high molecular lactic polyester thus produced was a brownishtransparent resin having a weight-average molecular weight of 340,000and a number-average molecular weight of 129,000. The high molecularlactic polyester exhibited a glass transition point of about 55° C., amelting point of about 155° C., a tensile break stress of 28%, a tensilebreak strength of 460 kgf/cm² and an initial tensile elasticity modulusof 11,000 kgf/cm².

EXAMPLE 10

27 mol % of an adipic acid component, 20 mol % of a succinic acidcomponent, 30 mol % of an ethylene glycol component, 20 mol % of aneopentyl glycol component and 0.3 mol % of a pyromellitic acidcomponent were charged. The reaction mixture was then esterified at atemperature of from 205° C. to 210° C. to have an acid value of 9.1. Tothe reaction mixture was then added 100 ppm of tetraisopropyl titanate.The reaction mixture was then allowed to undergo deglycolation reactionat a temperature of from 215° C. to 220° C., eventually under a pressureof 0.5 Torr, for 8 hours.

The aliphatic polyester thus obtained exhibited a weight-averagemolecular weight of 53,500 and a number-average molecular weight of16,500 (hereinafter referred to as "(P-4)"). To 30 parts of thepolyester thus obtained were then added 68 parts of L-lactide, 2 partsof D-lactide and 15 parts of toluene. These components were was thendissolved and mixed at a temperature of 175° C. in an atmosphere ofnitrogen gas for 0.25 hour. To the reaction mixture were then added 0.02part of tin octanoate as a ring opening polymerization catalyst. Thereaction mixture was then allowed to undergo reaction for 3 hours.

After reaction, toluene was removed under reduced pressure. The highmolecular lactic polyester thus produced was a colorless transparentresin having a weight-average molecular weight of 151,000 and anumber-average molecular weight of 101,000. The high molecular lacticpolyester exhibited a glass transition point of about 53° C., a meltingpoint of about 152° C., a tensile break stress of 270%, a tensile breakstrength of 400 kgf/cm² and an initial tensile elasticity modulus of7,800 kgf/cm².

EXAMPLE 11

In the present example, a final reaction vessel comprising a seriesconnection of three filling type 4-l capacity agitated reactors equippedwith a helical agitating blade and a reaction vessel connected to thefinal reaction vessel via a 1/2 inch static mixer (K onigs type staticmixer available from Noritake Co., Ltd.) and two degasification tankswere used.

The starting materials were supplied in the following manner. In somedetail, lactides and a hydroxyl-containing polymer were dissolved intoluene at a temperature of 110° C. in an atmosphere of nitrogen gas toobtain a 15% solution which was then supplied into the first reactor bymeans of a plunger pump in such a manner that the average residence timeof the starting materials was 8 hours. As the catalyst there was usedtin octanoate. This catalyst was added before the first reactor. Anaddition line was provided at the entrance of the third reaction vesselsuch that pyromellitic anhydride can be added to the material.

The supplied amount of these components were as follows:

Starting material supply flow rate: 1.5 l/hr.

Catalyst supply flow rate: 0.5 ml/hr.

Pyromellitic anhydride supply flow rate: 5.00 g/hr.

The lactide components and the hydroxyl-containing polymer componentsused were as follows:

L-lactide: 73%

D-lactide: 4%

Hydroxyl-containing polymer: 10%

Toluene: 13%

As the hydroxyl-containing polymer there was used a polyester comprising35 mol % of adipic acid, 15 mol % of succinic acid, 40 mol % of ethyleneglycol and 10 mol % of neopentyl glycol, having a weight-averagemolecular weight of 35,100 and a number-average molecular weight of18,200 (hereinafter referred to as "(P-5)").

Tin octanoate as a catalyst was supplied in such an amount that thecatalyst content reached 250 ppm. The polymer thus obtained wascontinuously withdrawn from the discharge end at the top of the finalreaction vessel by means of a gear pump.

The three reaction vessels used were temperature-controlled as follows:

Reaction temperature in first reaction vessel: 155° C.

Reaction temperature in second reaction vessel: 155° C.

Reaction temperature in third reaction vessel: 165° C.

Reaction temperature in the static mixer: 165° C.

Referring to the degasification conditions, the temperature of the heatexchanger provided before the first degasification apparatus wascontrolled to 220° C., and the degasification tank was evacuated to 110Torr. The temperature of the heat exchanger provided before the seconddegasification apparatus was controlled to 205° C., and thedegasification tank was evacuated to 8 Torr.

The polymer thus obtained was pelletized, and then measured for variousproperties and physical properties. The pellet thus obtained was aslightly yellowish transparent resin. The high molecular lacticpolyester thus produced was a colorless transparent resin having aweight-average molecular weight of 301,000 and a number-averagemolecular weight of 101,000. The high molecular lactic polyesterexhibited a glass transition point of about 53° C., a melting point ofabout 152° C., a tensile break stress of 28%, a tensile break strengthof 500 kgf/cm² and an initial tensile elasticity modulus of 11,800kgf/cm².

EXAMPLE 12

A continuous polymerization apparatus was used having a polymerizationzone consisting of a circulating polymerization line comprising a seriesconnection of four static mixers having an inner diameter of 0.5 in. anda length of 60 cm, equipped with a circulating gear pump, and apolymerization line comprising a series connection of two static mixershaving an inner diameter of 3/4 in. and a length of 50 cm (availablefrom Noritake Co., Ltd.; 15 mixing elements incorporated) directlyconnected to the circulating polymerization line.

The catalyst was mixed into the main starting material shortly beforethe main starting material supply pump by means of a static mixer havingan inner diameter of 1/4 in. and a length of 15.5 cm (available fromNoritake Co., Ltd.; 12 mixing elements incorporated).

A main starting material solution was prepared in an atmosphere ofnitrogen gas. In some detail, 78 parts of L-lactide, 4 parts ofD-lactide, 18 parts of a 50% toluene solution of an aliphatic polyesterwhich had been processed with trimellitic acid to have a highermolecular weight (29 mol % of adipic acid component, 20 mol % ofsuccinic acid component, 30 mol % of ethylene glycol component, 20 mol %of neopentyl glycol component, 0.3 mol % of trimellitic acid component;weight-average molecular weight: 53,500; number-average molecularweight: 16,500) (hereinafter referred to as "(P-6)"), and 0.04 part ofzinc 2-ethylhexanate as a catalyst were subjected to continuouspolymerization under the following conditions:

Main starting material supply flow rate: 400 ml/hr.

Catalyst supply flow rate: 1.6 ml/hr.

Reaction temperature: 160° C.

Rate of flow to be circulated in circulating polymerization line: 2l/hr.

Reflux ratio: 5

The polymer solution thus obtained was then introduced into an apparatuscomprising a heat exchanger and a degasification bath by an insulatedgear pump for high viscosity so that it was degasificated. Thetemperature of the heat exchanger provided before the degasificationapparatus was controlled to 200° C., and the degasification bath wasevacuated to 4 to 10 Torr. The high molecular lactic polyester thusobtained was a yellowish transparent resin. The resin was pelletized,and then measured for various properties and physical properties.

The result of GPC showed that a high molecular lactic polyester having aweight-average molecular weight of 368,000 had been produced. The highmolecular lactic polyester thus produced exhibited a glass transitionpoint of about 55° C., a melting point of about 152° C., a tensile breakstress of 30%, a tensile break strength of 490 kgf/cm² and an initialtensile elasticity modulus of 10,900 kgf/cm².

The high molecular lactic copolymer polyester thus pelletized was thenprocessed by a hot press to prepare a 10 cm wide×10 cm long×100 μm thicksheet.

In some detail, the pelletized polyester having a weight-averagemolecular weight of 368,000 was pressed at a temperature of 165° C.under a pressure of 200 kg/cm² for 2 minutes to obtain a sheet having aweight-average molecular weight of 355,000. The drop in the molecularweight was 3.5%.

The sheet thus obtained was then buried in the earth for biodegradationtest. The results are set forth in Table 1.

                  TABLE 1                                                         ______________________________________                                                   Weight-average                                                     Days of burial                                                                           molecular weight                                                                            Apperance                                            ______________________________________                                        0          355,000       Rigid, transparent                                   30         317,000       Rigid, semi-transparent                              100        181,000       Brittle, white                                       200         91,000       Brittle, white                                       ______________________________________                                    

EXAMPLE 13

To 99 parts of (P-2) were added 1 part of isophorone diisocyanate and100 parts of toluene as a solvent. The atmosphere of the system was thenreplaced by an inert gas. The reaction mixture was then allowed toundergo reaction at a temperature of 85° C. for 1.0 hour.

After reaction, toluene was removed under reduced pressure. The urethanebond-containing aromatic aliphatic polyester as a starting materialexhibited a weight-average molecular weight of 98,300 and anumber-average molecular weight of 41,900 and showed a single GPC peakdemonstrating the production of a single product. To 5 parts of theurethane bond-containing aromatic aliphatic polyester as a startingmaterial were then added 93 parts of L-lactide and 2 parts of D-lactide.The atmosphere of the system was then replaced by an inert gas. Thesecomponents were then dissolved and mixed at a temperature of 110° C. for1 hour. To the reaction mixture was then added 200 ppm of tin octanoateas a ring opening polymerization catalyst.

Thereafter, the reaction mixture was allowed to undergo reaction at atemperature of 165° C. for 1.5 hours. The resulting copolymercomposition was then withdrawn. The urethane bond-containing lacticpolyester thus obtained was a brownish transparent resin. The result ofGPC showed that an urethane bond-containing lactic polyester having aweight-average molecular weight of 291,000 and a number-averagemolecular weight of 142,000 had been produced. The product showed asingle GPC peak demonstrating the production of a single copolymer. 2.4%of the lactide monomer remained. The result of DSC showed that theurethane bond-containing lactic polyester exhibits a glass transitionpoint of 55° C. and a melting point of 173° C. The urethanebond-containing lactic polyester also exhibited a tensile break stressof 39%, a tensile break strength of 430 kgf/cm², an initial tensileelasticity modulus of 12,000 kgf/cm² and a Vicat softening temperatureof 51° C.

EXAMPLE 14

To 5 parts of (P-1) were added 93 parts of L-lactide and 2 parts ofD-lactide. The atmosphere of the system was then replaced by an inertgas. These components were then dissolved and mixed at a temperature of165° C. for 1 hour. To the reaction mixture was then added 0.02 part oftin octanoate as a ring opening polymerization catalyst. The reactionmixture was then allowed to undergo reaction for 8 hours.

The lactic polyester thus obtained was a colorless transparent resin.The result of GPC showed that a lactic polyester having a weight-averagemolecular weight of 144,400 had been produced. To 99 parts of the lacticpolyester were then added 1 part of Pandex P-870 (available fromDainippon Ink & Chemicals, Inc.; NCO%=3.0) and 100 parts of toluene as asolvent. The atmosphere of the system was then replaced by an inert gas.To the reaction mixture were then added 50 ppm of tetraethylammoniumchloride as a catalyst. The reaction mixture was then allowed to undergoreaction at a temperature of 90° C. for 1 hour.

Thereafter, the reaction mixture was allowed to undergo reaction at atemperature of 165° C. for 1.5 hours. The resulting copolymercomposition was then withdrawn. The urethane bond-containing lacticpolyester thus obtained was a whitish transparent resin. The result ofGPC showed that an urethane bond-containing lactic polyester having aweight-average molecular weight of 275,000 had been produced. Theproduct showed a single GPC peak demonstrating the production of asingle copolymer. 2.8% of the lactide monomer remained. The result ofDSC showed that the urethane bond-containing lactic polyester exhibits aglass transition point of 54° C. and a melting point of 161° C. Theurethane bond-containing lactic polyester also exhibited a tensile breakstress of 72%, a tensile break strength of 400 kgf/cm², an initialtensile elasticity modulus of 11,000 kgf/cm² and a Vicat softeningtemperature of 50° C.

EXAMPLE 15

In the present example, a final reaction vessel comprising a seriesconnection of three filling type 4-l capacity agitated reactors equippedwith a helical agitating blade and a reaction vessel connected to thefinal reaction vessel via a 1/2 inch static mixer (K onigs type staticmixer available from Noritake Co., Ltd.) and two degasification tankswere used.

The starting materials were supplied in the following manner. In somedetail, lactides and a hydroxyl-containing polymer were dissolved intoluene at a temperature of 110° C. in an atmosphere of nitrogen gas toobtain a 15% solution which was then supplied into the first reactor bymeans of a plunger pump in such a manner that the average residence timeof the starting materials was 8 hours. As the catalyst there was usedtin octanoate. This catalyst was added before the first reactor. Anaddition line was provided at the entrance of the third reaction vesselsuch that Pandex P-870 (Dainippon Ink & Chemicals, Inc.; NCO%=3.0) canbe added to the material.

The supplied amount of these components were as follows:

Starting material supply flow rate: 1.5 l/hr.

Catalyst supply flow rate: 0.5 ml/hr.

Pandex P-870 supply flow rate: 5.0 g/hr.

The lactide components and the hydroxyl-containing polymer componentsused were as follows:

L-lactide: 73%

D-lactide: 4%

Hydroxyl-containing polymer: 10%

Toluene: 13%

As the hydroxyl-containing polymer there was used (P-5). Tin octanoateas a catalyst was supplied in such an amount that the catalyst contentreached 250 ppm. The polymer thus obtained was continuously withdrawnfrom the discharge end at the top of the final reaction vessel by meansof a gear pump.

The three reaction vessels used were temperature-controlled as follows:

Reaction temperature in first reaction vessel: 155° C.

Reaction temperature in second reaction vessel: 155° C.

Reaction temperature in third reaction vessel: 165° C.

Reaction temperature in the static mixer: 165° C.

Referring to the degasification conditions, the temperature of the heatexchanger provided before the first degasification apparatus wascontrolled to 220° C., and the degasification tank was evacuated to 110Torr. The temperature of the heat exchanger provided before the seconddegasification apparatus was controlled to 205° C., and thedegasification tank was evacuated to 8 Torr.

The polymer thus obtained was pelletized, and then measured for variousproperties and physical properties. The pellet thus obtained was aslightly yellowish transparent resin. The high molecular lacticpolyester thus produced was a colorless transparent resin having aweight-average molecular weight of 416,000 and a number-averagemolecular weight of 202,000. The high molecular lactic polyesterexhibited a glass transition point of about 52° C., a melting point ofabout 156° C., a tensile break stress of 58%, a tensile break strengthof 470 kgf/cm², an initial tensile elasticity modulus of 11,000 kgf/cm²and a Vicat softening temperature of 50° C.

EXAMPLE 16

A continuous polymerization apparatus was used having a polymerizationzone consisting of a circulating polymerization line comprising a seriesconnection of four static mixers having an inner diameter of 0.5 in. anda length of 60 cm, equipped with a circulating gear pump, and apolymerization line comprising a series connection of two static mixershaving an inner diameter of 3/4 in. and a length of 50 cm (availablefrom Noritake Co., Ltd.; 15 mixing elements incorporated) directlyconnected to the circulating polymerization line.

The catalyst was mixed into the main starting material shortly beforethe main starting material supply pump by means of a static mixer havingan inner diameter of 1/4 in. and a length of 15.5 cm (available fromNoritake Co., Ltd.; 12 mixing elements incorporated).

A main starting material solution was prepared in an atmosphere ofnitrogen gas. In some detail, 78 parts of L-lactide, 4 parts ofD-lactide, 18 parts of a 50% toluene solution of an aliphatic polyesterwhich had been processed with hexamethylene diisocyanate to have ahigher molecular weight (29 mol % of adipic acid component, 20 mol % ofsuccinic acid component, 30 mol % of ethylene glycol component, 20 mol %of neopentyl glycol component, 0.5 mol % of hexamethylene diisocyanatecomponent; weight-average molecular weight: 62,100; number-averagemolecular weight: 26,500) (hereinafter referred to as "(P-7)"), and 0.04part of zinc 2-ethylhexanate as a catalyst were subjected to continuouspolymerization under the following conditions:

Main starting material supply flow rate: 400 ml/hr.

Catalyst supply flow rate: 1.6 ml/hr.

Reaction temperature: 160° C.

Rate of flow to be circulated in circulating polymerization line: 2l/hr.

Reflux ratio: 5

The polymer solution thus obtained was then introduced into an apparatuscomprising a heat exchanger and a degasification bath by an insulatedgear pump for high viscosity so that it was degasificated. Thetemperature of the heat exchanger provided before the degasificationapparatus was controlled to 200° C., and the degasification bath wasevacuated to 4 to 10 Torr. The high molecular lactic polyester thusobtained was a yellowish transparent resin. The resin was pelletized,and then measured for various properties and physical properties.

The result of GPC showed that a high molecular lactic copolymerpolyester having a weight-average molecular weight of 404,000 and anumber-average molecular weight of 208,000 had been produced. The highmolecular lactic polyester thus produced exhibited a glass transitionpoint of about 56° C., a melting point of about 158° C., a tensile breakstress of 40%, a tensile break strength of 500 kgf/cm², an initialtensile elasticity modulus of 14,000 kgf/cm² and a Vicat softeningtemperature of 52° C.

EXAMPLE 17

To 98 parts of (P-1) were added 2 parts of toluene-2,4-diisocyanate and100 parts of toluene as a solvent. The atmosphere of the system was thenreplaced by an inert gas. The reaction mixture was then allowed toundergo reaction at a temperature of 85° C. for 1.0 hour.

After reaction, toluene was removed under reduced pressure. The urethanebond-containing aromatic aliphatic polyester as a starting materialexhibited a weight-average molecular weight of 111,000 and anumber-average molecular weight of 43,000 and showed a single GPC peakdemonstrating the production of a single product. To 30 parts of theurethane bond-containing aromatic aliphatic polyester as a startingmaterial were then added 68 parts of L-lactide and 2 parts of D-lactide.The atmosphere of the system was then replaced by an inert gas. Thesecomponents were then dissolved and mixed at a temperature of 110° C. for1 hour. To the reaction mixture was then added 200 ppm of tin octanoateas a ring opening polymerization catalyst.

Thereafter, the reaction mixture was allowed to undergo reaction at atemperature of 165° C. for 1.5 hours. The resulting copolymercomposition was then withdrawn. The urethane bond-containing lacticpolyester thus obtained was a brownish transparent resin. The result ofGPC showed that an urethane bond-containing lactic polyester having aweight-average molecular weight of 152,000 and a number-averagemolecular weight of 88,000 had been produced. The product showed asingle GPC peak demonstrating the production of a single copolymer. 1.8%of the lactide monomer remained. The result of DSC showed that theurethane bond-containing lactic polyester exhibits a glass transitionpoint of 50° C. and a melting point of 162° C. The urethanebond-containing lactic polyester also exhibited a tensile break stressof 310%, a tensile break strength of 280 kgf/cm², an initial tensileelasticity modulus of 9,000 kgf/cm² and a Vicat softening temperature of49° C.

EXAMPLE 18

To 30 parts of (P-1) were added 70 parts of L-lactide. These componentswere then dissolved and mixed at a temperature of 165° C. for 1 hour inan atmosphere of an inert gas. To the reaction mixture was then added0.02 part of tin octanoate as a ring opening polymerization catalyst.The reaction mixture was then allowed to undergo reaction for 8 hours.

The lactic polyester thus obtained was a colorless transparent resin.The result of GPC showed that a lactic polyester having a weight-averagemolecular weight of 73,000 had been produced. To 99 parts of the lacticpolyester were then added 1 part oftriphenylmethane-4,4',4"-triisocyanate and 100 parts of toluene as asolvent. The atmosphere of the system was then replaced by an inert gas.To the reaction mixture were then added 50 ppm of tetraethylammoniumchloride as a catalyst. The reaction mixture was then allowed to undergoreaction at a temperature of 90° C. for 1 hour.

Thereafter, the reaction mixture was allowed to undergo reaction at atemperature of 165° C. for 1.5 hours. The resulting copolymercomposition was then withdrawn. The urethane bond-containing lacticpolyester thus obtained was a whitish transparent resin. The result ofGPC showed that an urethane bond-containing lactic polyester having aweight-average molecular weight of 147,000 and a number-averagemolecular weight of 55,000 had been produced. The product showed asingle GPC peak demonstrating the production of a single copolymer. 2.0%of the lactide monomer remained. The result of DSC showed that theurethane bond-containing lactic polyester exhibits a glass transitionpoint of 49° C. and a melting point of 161° C. The urethanebond-containing lactic polyester also exhibited a tensile break stressof 280%, a tensile break strength of 300 kgf/cm², an initial tensileelasticity modulus of 9,900 kgf/cm² and a Vicat softening temperature of47° C.

EXAMPLE 19

The pellet obtained in Example 14 was thoroughly dried, and thenextruded through an extruder equipped with a screw having L/D of 24 anda diameter of 50 mm (available from Tanabe Plastic Co., Ltd.) at anextrusion temperature of 190° C. to obtain a 0.15-mm thick sheet havinga good transparency. The extrusion was effected at a screw revolutionspeed of 24 rpm, a discharge rate of 16 kg/hr, a back pressure of 86kg/cm² and a take-off speed of 6.0 m/min.

EXAMPLE 20

The 0.15-mm sheet obtained in Example 17 was formed by a vacuum formingmachine (available from Sanwa Kogyo K.K.). In some detail, the sheet washeated for 5 seconds, formed and cooled for 5 seconds, and then releasedfrom the mold in 1 second to form a tray cover for dish. As a result, aformed product having an excellent mold reproducibility and transparencywas obtained.

EXAMPLE 21

The pellet obtained in Example 1 was thoroughly dried, and thenblow-molded by a blow molding machine equipped with an extruder having ascrew having L/D of 25 and a diameter of 40 mm (produced by The JapanSteel Works, Ltd.) to obtain a 60 ml bottle having an excellent moldreproducibility and transparency. In some detail, the pellet wasblow-molded at a cylinder temperature of from 170° C. to 180° C., acylinder head temperature of 180° C., a mold temperature of 32° C. and adischarge rate of 4.2 kg/hr with air blown therethrough from the diecore at a rate of 3 kgf/cm².

EXAMPLE 22

The pellet obtained in Example 4 was thoroughly dried, extruded througha 50-mm extruder equipped with a 400-mm wide die, and then laminated ona paper having a weight of 200 g/m². In some detail, the pellet wasextruded at a cylinder temperature of from 150° C. to 210° C., a dietemperature of 210° C., a cooling roll temperature of 60° C., adischarge rate of 4 kg/hr, and a line speed of 10 m/min.

The laminated paper thus obtained exhibited a uniform thickness and alaminate strength as high as not less than 370 g/15 mm.

COMPARATIVE EXAMPLE 1

To 100 parts of L-lactide were added 15 parts of toluene. The mixturewas dissolved and stirred at a temperature of 175° C. in an atmosphereof nitrogen gas for 0.5 hour. To the reaction mixture were then added0.02 part of tin octanoate as a ring opening polymerization catalyst.The reaction mixture was then allowed to undergo polymerization for 3hours. After reaction, toluene was removed under reduced pressure. Thepoly(L-lactic acid) thus obtained was a colorless transparent resinhaving a weight-average molecular weight of 273,000 and a number-averagemolecular weight of 140,000. The resin exhibited a glass transitionpoint of about 57° C., a melting point of about 158° C., a tensile breakstress of 6.0%, a tensile break strength of 450 kgf/cm² and an initialtensile elasticity modulus of 11,000 kgf/cm².

COMPARATIVE EXAMPLE 2

To 70 parts of L-lactide were added 30 parts of a polycaprolactone("Tone", available from UCC) and 15 parts of toluene. The mixture wasdissolved and stirred at a temperature of 175° C. in an atmosphere ofnitrogen gas for 0.5 hour. To the reaction mixture were then added 0.02part of tin octanoate as a ring opening polymerization catalyst. Thereaction mixture was then allowed to undergo polymerization for 3 hours.After reaction, toluene was removed under reduced pressure. The lacticcopolymer polyester thus obtained was a white resin having aweight-average molecular weight of 123,000 and a number-averagemolecular weight of 62,000. The resin exhibited a glass transition pointof about 30° C., a melting point of about 149° C., a tensile breakstress of 100%, a tensile break strength of 320 kgf/cm² and an initialtensile elasticity modulus of 6,800 kgf/cm².

COMPARATIVE EXAMPLE 3

To 10 parts of (P-1) were added 90 parts of L-lactide and 20 parts oftoluene. The mixture was dissolved and stirred at a temperature of 175°C. in an atmosphere of nitrogen gas for 0.5 hour. To the reactionmixture were then added 0.02 part of tin octanoate as a ring openingpolymerization catalyst. The reaction mixture was then allowed toundergo polymerization for 3 hours. After reaction, toluene was removedunder reduced pressure. The lactic copolymer polyester thus obtained wasa colorless transparent resin having a weight-average molecular weightof 140,000 and a number-average molecular weight of 81,000. The resinexhibited a glass transition point of about 47° C., a melting point ofabout 156° C., a tensile break stress of 12%, a tensile break strengthof 450 kgf/cm² and an initial tensile elasticity modulus of 10,000kgf/cm².

COMPARATIVE EXAMPLE 4

To 20 parts of (P-1) were added 70 parts of L-lactide, 10 parts ofD-lactide and 20 parts of toluene. The mixture was dissolved and stirredat a temperature of 175° C. in an atmosphere of nitrogen gas for 0.5hour. To the reaction mixture were then added 0.02 part of tin octanoateas a ring opening polymerization catalyst. The reaction mixture was thenallowed to undergo polymerization for 3 hours. After reaction, toluenewas removed under reduced pressure. The lactic copolymer polyester thusobtained was a colorless transparent resin having a weight-averagemolecular weight of 110,000 and a number-average molecular weight of63,200. The resin exhibited a glass transition point of about 44° C., amelting point of about 154° C., a tensile break stress of 21%, a tensilebreak strength of 390 kgf/cm² and an initial tensile elasticity modulusof 7,600 kgf/cm².

COMPARATIVE EXAMPLE 5

To 30 parts of (P-1) were added 68 parts of L-lactide, 2 parts ofD-lactide and 20 parts of toluene. The mixture was dissolved and stirredat a temperature of 165° C. in an atmosphere of nitrogen gas for 0.5hour. To the reaction mixture were then added 0.03 part of tin octanoateas a ring opening polymerization catalyst. The reaction mixture was thenallowed to undergo polymerization for 3 hours. After reaction, toluenewas removed under reduced pressure. The lactic copolymer polyester thusobtained was a colorless transparent resin having a weight-averagemolecular weight of 78,000 and a number-average molecular weight of41,000. The resin exhibited a glass transition point of about 38° C., amelting point of about 146° C., a tensile break stress of 40%, a tensilebreak strength of 300 kgf/cm² and an initial tensile elasticity modulusof 5,800 kgf/cm².

COMPARATIVE EXAMPLE 6

To 5 parts of (P-2) were added 93 parts of L-lactide, 2 parts ofD-lactide and 20 parts of toluene. The mixture was dissolved and stirredat a temperature of 175° C. in an atmosphere of nitrogen gas for 0.5hour. To the reaction mixture were then added 0.03 part of tin octanoateas a ring opening polymerization catalyst. The reaction mixture was thenallowed to undergo polymerization for 3 hours. After reaction, toluenewas removed under reduced pressure. The lactic copolymer polyester thusobtained was a colorless transparent resin having a weight-averagemolecular weight of 161,000 and a number-average molecular weight of83,200. The resin exhibited a glass transition point of about 46° C., amelting point of about 154° C., a tensile break stress of 7.7%, atensile break strength of 410 kgf/cm² and an initial tensile elasticitymodulus of 7,500 kgf/cm².

COMPARATIVE EXAMPLE 7

To 30 parts of (P-1) were added 70 parts of L-lactide and 15 parts oftoluene. The mixture was dissolved and stirred at a temperature of 165°C. in an atmosphere of nitrogen gas for 0.5 hour. To the reactionmixture were then added 0.03 part of tin octanoate as a ring openingpolymerization catalyst. The reaction mixture was then allowed toundergo polymerization for 3 hours. After reaction, toluene was removedunder reduced pressure. The lactic copolymer polyester thus obtained wasa colorless transparent resin having a weight-average molecular weightof 73,000 and a number-average molecular weight of 37,000. The resinexhibited a glass transition point of about 45° C., a melting point ofabout 151° C., a tensile break stress of 78%, a tensile break strengthof 400 kgf/cm² and an initial tensile elasticity modulus of 7,600kgf/cm².

COMPARATIVE EXAMPLE 8

To 5 parts of (P-1) were added 93 parts of L-lactide, 2 parts ofD-lactide and 20 parts of toluene. The mixture was dissolved and stirredat a temperature of 175° C. in an atmosphere of nitrogen gas for 0.5hour. To the reaction mixture were then added 0.03 part of tin octanoateas a ring opening polymerization catalyst. The reaction mixture was thenallowed to undergo polymerization for 3 hours. After reaction, toluenewas removed under reduced pressure. The lactic copolymer polyester thusobtained was a colorless transparent resin having a weight-averagemolecular weight of 144,000 and a number-average molecular weight of73,000. The resin exhibited a glass transition point of about 44° C., amelting point of about 153° C., a tensile break stress of 3.5%, atensile break strength of 400 kgf/cm² and an initial tensile elasticitymodulus of 10,500 kgf/cm².

The results oil the measurement of various properties and TG/DTA (weightloss) of the lactic copolymer polyesters obtained in the foregoingexamples and comparative examples are set forth in Tables 2 to 8. Thefollowing abbreviations will be used in these tables.

Trimellitic acid: TM

Trimellitic anhydride: TMA

Pyromellitic acid: PM

Pyromellitic anhydride: PMDA

                  TABLE 2                                                         ______________________________________                                        Materials or   Exam-   Exam-   Exam-                                          properties     ple 1   ple 2   ple 3 Example 4                                ______________________________________                                        Starting material                                                             L-LD (parts)   90      93      68    93                                       D-LD (parts)   0       2       2     2                                        Polyester      P-1     P-2     P-1   P-2                                      (parts)        10      5       30    5                                        Mw × 1000.sup.-1                                                                       30.2    45.2    30.2  45.2                                     Polyvalent     PMDA    PMDA    TMA   PMDA                                     carboxylic acid                                                                              0.002   0.05    1     0.002                                    (parts)                                                                       Mw × 1000.sup.-1                                                                       315     356     110   517                                      % Weight loss  1.5     1.7     7.7   2.9                                      Glass transition                                                                             56      58      53    59                                       point (°C.)                                                            Tensile break stress (%)                                                                     41      9.6     230   12                                       Tensile break strength                                                                       520     650     490   550                                      (kgf/cm.sup.2)                                                                Initial tensile elasticity                                                                   10,100  13,000  8,100 11,900                                   modulus (kgf/cm.sup.2)                                                        ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Materials or   Exam-   Exam-   Exam-                                          properties     ple 5   ple 6   ple 7 Example 8                                ______________________________________                                        Starting material                                                             L-LD (parts)   70      93      70    93                                       D-LD (parts)   0       2       10    2                                        Polyester      P-1     P-1     P-1   P-2                                      (parts)        30      5       20    5                                        Mw × 1000.sup.-1                                                                       30.2    30.2    30.2  45.2                                     Polyvalent     PMDA    PMDA    TMA   PMDA                                     carboxylic acid                                                                              0.05    0.5     0.002 0.05                                     (parts)                                                                       Mw × 1000.sup.-1                                                                       145     327     168   325                                      % Weight loss  7.5     2.2     7.8   3.4                                      Glass transition                                                                             54      57      51    56                                       point (°C.)                                                            Tensile break stress (%)                                                                     330     18      180   27                                       Tensile break strength                                                                       470     510     420   560                                      (kgf/cm.sup.2)                                                                Initial tensile elasticity                                                                   8,200   13,000  7,900 12,000                                   modulus (kgf/cm.sup.2)                                                        ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Materials or   Exam-   Exam-   Exam-                                          properties     ple 9   ple 10  ple 11                                                                              Example 12                               ______________________________________                                        Starting material                                                             L-LD (parts)   90      68      84    86                                       D-LD (parts)   0       2       5     4                                        Polyester      P-3     P-4     P-5   P-6                                      (parts)        10      30      11    10                                       Mw × 1000.sup.-1                                                                       118     53.5    35.1  53.5                                     Polyvalent     PMDA    PM      PMDA  TM                                       carboxylic acid                                                                              0.14    1       0.3   1                                        (parts)                                                                       Mw × 1000.sup.-1                                                                       340     151     301   368                                      % Weight loss  3.3     8.1     3.9   4.2                                      Glass transition                                                                             55      53      53    55                                       point (°C.)                                                            Tensile break stress                                                                         28      270     28    30                                       (%)                                                                           Tensile break strength                                                                       460     400     500   490                                      (kgf/cm.sup.2)                                                                Initial tensile elasticity                                                                   11,000  7,800   11,800                                                                              10,900                                   modulus (kgf/cm.sup.2)                                                        ______________________________________                                    

                                      TABLE 5                                     __________________________________________________________________________    Materials or                                                                  Properties  Example 13                                                                           Example 14                                                                          Example 14                                                                          Example 16                                     __________________________________________________________________________    Starting material                                                             L-LD (parts)                                                                              93     93    84    86                                             D-LD (parts)                                                                              2      2     5     4                                              Polyester   P-2    P-1   P-5   P-7                                            (parts)     5      5     11    10                                             Mw × 1000.sup.-1                                                                    45.2   30.2  35.1  62.1                                           Polyvalent  Isophorone                                                                           Pandex                                                                              Pandex                                                                              Hexamethylene                                  isocyanate  diisocyanate                                                                         P-870 P-870 diisocyanate                                   (parts)     1      1     0.4   1.3                                            Mw × 1000.sup.-1                                                                    291    275   416   404                                            % Weight loss                                                                             4.9    3.2   3.1   3.8                                            Glass transition                                                                          55     54    52    56                                             point (°C.)                                                            Tensile break stress                                                                      39     72    58    40                                             (%)                                                                           Tensile break strength                                                                    430    400   470   500                                            (kgf/cm.sup.2)                                                                Initial tensile                                                                           12,000 11,000                                                                              11,000                                                                              14,000                                         elasticity                                                                    modulus (kg/cm.sup.2)                                                         Vicat softening                                                                           51     50    50    52                                             temperature (°C.)                                                      __________________________________________________________________________

                  TABLE 6                                                         ______________________________________                                        Materials or                                                                  properties     Example 17  Example 18                                         ______________________________________                                        Starting material                                                             L-LD (parts)   68          70                                                 D-LD (parts)   2           0                                                  Polyester      P-1         P-1                                                (parts)        30          30                                                 Mw × 1000.sup.-1                                                                       30.2        30.2                                               Polyvalent     Toluene-2,4-                                                                              Triphenylmethane                                   isocyanate     diisocyanate                                                                              triisocyanate                                      (parts)        2           1                                                  Mw × 1000.sup.-1                                                                       152         147                                                % Weight loss  3.9         2.8                                                Glass transition                                                                             50          49                                                 point (°C.)                                                            Tensile break stress                                                                         310         280                                                (%)                                                                           Tensile break strength                                                                       280         300                                                (kgf/cm.sup.2)                                                                Initial tensile                                                                              9,000       9,900                                              elasticity                                                                    modulus (kg/cm.sup.2)                                                         Vicat softening                                                                              49          47                                                 temperature (°C.)                                                      ______________________________________                                    

                                      TABLE 7                                     __________________________________________________________________________    Materials or                                                                              Comparative                                                                          Comparative                                                                          Comparative                                                                          Comparative                                  properties  Example 1                                                                            Example 2                                                                            Example 3                                                                            Example 4                                    __________________________________________________________________________    Starting material                                                             L-LD (parts)                                                                              100    70     90     70                                           D-LD (parts)                                                                              0      0      0      10                                           Polyester   --     Tone   P-1    P-1                                          (parts)     --     30     10     20                                           Mw × 1000.sup.-1                                                                    --     --     30.2   30.2                                         Mw × 1000.sup.-1                                                                    273    123    140    110                                          % Weight loss                                                                             10.3   15.1   9.9    12.1                                         Glass transition                                                                          57     30     47     44                                           point (°C.)                                                            Tensile break stress                                                                      6.0    100    12     21                                           (%)                                                                           Tensile break strength                                                                    450    320    450    390                                          (kgf/cm.sup.2)                                                                Initial tensile                                                                           11,000 6,800  10,000 7,600                                        elasticity                                                                    modulus (kg/cm.sup.2)                                                         __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________    Materials or                                                                              Comparative                                                                          Comparative                                                                          Comparative                                                                          Comparative-                                 properties  Example 5                                                                            Example 6                                                                            Example 7                                                                            Example 8                                    __________________________________________________________________________    Starting material                                                             L-LD (parts)                                                                              68     93     70     93                                           D-LD (parts)                                                                              2      2      0      2                                            Polyester   P-1    P-2    P-1    P-1                                          (parts)     30     5      30     5                                            Mw × 1000.sup.-1                                                                    30.2   45.2   30.2   30.2                                         Mw × 1000.sup.-1                                                                    78     161    73     145                                          % Weight loss                                                                             10.9   11.3   10.5   9.1                                          Glass transition                                                                          38     46     45     44                                           point (°C.)                                                            Tensile break stress                                                                      40     7.7    78     3.5                                          (%)                                                                           Tensile break strength                                                                    300    410    400    400                                          (kgf/cm.sup.2)                                                                Initial tensile                                                                           5,800  7,500  7,600  10,500                                       elasticity                                                                    modulus (kg/cm.sup.2)                                                         __________________________________________________________________________

The present invention can provide a process for the preparation of abiodegradable high molecular lactic polyester which exhibits asufficiently high molecular weight and heat resistance and shows asufficient rigidity, flexibility and transparency depending on thepurpose.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A process for the preparation of a high molecular lactic copolymer polyester, which comprises allowing a lactide (A), a polyester terminated by hydroxyl group at both ends (B1), a polyvalent carboxylic acid having 3 or more functionalities and/or acid anhydride thereof (C) to undergo ring opening copolymerization in such an amount that the weight ratio of (A)/(B1) is from 50/50 to 98/2 and the proportion of the component (C) is from 0.001 to 5% by weight of the sum of the amount of the components (A) and (B1) in the presence of a ring opening polymerization catalyst (D).
 2. A process for the preparation of a high molecular lactic copolymer polyester, which comprises allowing a lactide (A) and a polyester terminated by hydroxyl group at both ends (B1) to undergo ring opening copolymerization in (A)/(B1) weight ratio of 50/50 to 98/2 in the presence of a ring opening polymerization catalyst (D) to prepare a polyester, and then reacting said polyester with a polyvalent carboxylic acid having 3 or more functionalities and/or acid anhydride thereof (C) in such an amount that the proportion of the component (C) is from 0.001 to 5% by weight of the sum of the amount of the components (A) and (B1).
 3. A process for the preparation of a high molecular lactic copolymer polyester, which comprises reacting a polyester terminated by hydroxyl group at both ends (B1) with a polyvalent carboxylic acid having 3 or more functionalities and/or acid anhydride thereof (C) in such an amount that the proportion of the component (C) is from 0.001 to 5% by weight of the amount of the component (B1) to obtain a polyester terminated by hydroxyl group at both ends having a weight-average molecular weight of from 10,000 to 300,000 (B2), and then allowing said polyester (B2) and a lactide (A) to undergo ring opening copolymerization in such an amount that the weight ratio of (A)/(B2) is from 50/50 to 98/2 in the presence of a ring opening polymerization catalyst (D).
 4. A process for the preparation of a high molecular lactic copolymer polyester, which comprises allowing a dicarboxylic acid, a diol and a polyvalent carboxylic acid having 3 or more functionalities and/or acid anhydride thereof (C) in an amount of from 0.001 to 5% by weight to undergo dehydration reaction and/or deglycolation reaction to obtain a polyester having a weight-average molecular weight of from 10,000 to 300,000 (B3), and then allowing said polyester (B3) and a lactide (A) to undergo ring opening copolymerization in such an amount that the weight ratio of (A)/(B3) is from 50/50 to 98/2 in the presence of a ring opening polymerization catalyst (D).
 5. The process for the preparation of a high molecular lactic copolymer polyester according to any one of claims 1 to 3, wherein said polyester terminated by hydroxyl group at both ends (B1) has a weight-average molecular weight of 10,000 to 200,000.
 6. The process for the preparation of a high molecular lactic copolymer polyester according to any one of claims 1 to 4, wherein said polyvalent carboxylic acid having 3 or more functionalities and/or acid anhydride thereof (C) is selected from the group consisting of trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic anhydride.
 7. The process for the preparation of a high molecular lactic copolymer polyester according to any one of claims 1 to 4, wherein the resulting high molecular lactic copolymer polyester has a weight-average molecular weight of from 20,000 to 600,000.
 8. The process for the preparation of a high molecular lactic copolymer polyester according to any one of claims 1 to 4, wherein a static mixer is used as a polymerization reaction vessel.
 9. The process for the preparation of a high molecular lactic copolymer polyester according to any one of claims 1 to 4, wherein a continuous polymerization apparatus comprising a series connection of two or more agitated reaction vessels is used.
 10. A formed or molded product of a high molecular lactic copolymer polyester prepared by the preparation process according to any one of claims 1 to
 4. 